CN1732408B - Radiation sensitive resin composition - Google Patents

Radiation sensitive resin composition Download PDF

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Publication number
CN1732408B
CN1732408B CN2003801077532A CN200380107753A CN1732408B CN 1732408 B CN1732408 B CN 1732408B CN 2003801077532 A CN2003801077532 A CN 2003801077532A CN 200380107753 A CN200380107753 A CN 200380107753A CN 1732408 B CN1732408 B CN 1732408B
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methyl
acid
compound
carbon number
repetitive
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CN1732408A (en
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西村功
藤原考一
小林英一
下川努
中村敦
米田英司
王勇
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JSR Corp
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0046—Photosensitive materials with perfluoro compounds, e.g. for dry lithography
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
    • G03F7/0397—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition the macromolecular compound having an alicyclic moiety in a side chain
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor
    • G03F7/2002—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image
    • G03F7/2004—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image characterised by the use of a particular light source, e.g. fluorescent lamps or deep UV light
    • G03F7/2006—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image characterised by the use of a particular light source, e.g. fluorescent lamps or deep UV light using coherent light; using polarised light

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  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Materials For Photolithography (AREA)
  • Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
  • Polymerization Catalysts (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

A radiation-sensitive resin composition comprising: a resin having acid-dissociable groups which is insoluble or sparingly soluble in alkalis, has a specific structure that makes the resin alkali-soluble by the action of an acid, and is obtained by living radical polymerization; and a radiation-sensitive acid generator, wherein the ratio of the weight-average molecular weight to the number-average molecular weight of the resin having acid-dissociable groups [(weight-average molecular weight)/(number-average molecular weight)] is 1.5 or lower.

Description

Radiation-sensitive resin composition
Technical field
The present invention relates to a kind of radiation-sensitive resin composition, particularly relate to and a kind ofly can be suitable as the chemically amplified corrosion-resisitng agent radiation-sensitive resin composition useful to microfabrication, this microfabrication uses the X of far ultraviolet, synchrotron radioactive ray etc. such as KrF excimer laser or ArF excimer laser to penetrate the various radioactive ray of charged particle rays such as light, electron ray and so on.
Background technology
In the micro processing field that is fabricated to representative,, use ArF excimer laser (wavelength 193nm), F recently in order to obtain higher integrated level with integrated circuit component 2It is necessary with the lithography of lower horizontal microfabrication that excimer laser (wavelength 157nm) etc. can carry out the 200nm size.As the radiation-sensitive resin composition that is suitable for utilizing such excimer laser to shine, proposed much the applications about the chemical amplifying type radiation-sensitive resin composition, this chemical amplifying type radiation-sensitive resin composition has utilized by the composition with acid dissociation functional group and has been the chemical amplification effect that acid producing agent obtains by the acidic composition of radiation exposure.
For example; patent documentation 1 discloses the chemical amplification type positive resist composition as radiation-sensitive resin composition; this eurymeric resist composition contains the alkali solubility with 2-alkyl-2-adamantane radical base or 1-adamantyl-1-alkyl adamantane protection; himself being the insoluble or indissoluble of alkali, is acid producing agent but the effect by acid becomes the resin and the specific sulfonium salt of alkali ease of solubility.Patent documentation 2 discloses a kind of photoresist macromolecular compound of 3 yuan of copolymerization, this macromolecular compound is to add as ternary specific alicyclic esters with intermediate polarity of above-mentioned two kinds of compositions in the ester of specific base plate bonding alicyclic esters and the acidolysis absorption with specific alicyclic ring skeleton, disclose a kind of resin that contains 3 kinds of monomeric units of the ad hoc structure with identical alicyclic ring skeleton with special ratios in the patent documentation 3, these are known.
[patent documentation 1] spy opens 2002-156750 communique (claim)
[patent documentation 2] spy opens 2002-145955 communique (claim)
[patent documentation 3] spy opens 2002-201232 communique (claim)
But, at semiconductor applications, if obtain must make radiation-sensitive resin composition have better resolution as resist than higher now integrated level.And then, requirement has been proposed the contributive raw material repeatable accuracy of batch deviation on making for fine pattern formation.And when often discovery was carried out the operation of more miniaturization simultaneously, the small shortcoming that produces during development can become the example of fatal defective in device design.In order to handle such situation, must improve the exploitation of the processing tolerance limit of resist resolution and exposure interdependence etc. at present, but the tiny flaw that produces when considering to develop results from as the resin of constituent, and the task of top priority is to improve its dissolubility in the resist solvent.
Summary of the invention
The objective of the invention is in order to solve such problem, a kind of radiation-sensitive resin composition is provided, it has (methyl) acrylic acid series polymeric compounds and its multipolymer that specified molecular weight distributes by use, not only the transparency to radioactive ray is high to make it, and susceptibility, resolution, anti-dry corrosion, pattern form etc. are also good as the basic physical properties of resist, particularly the dissolubility to the resist solvent is good, in the roughness that reduces the pattern sidewalls after developing, improved and made stability.
Radiation-sensitive resin composition of the present invention is to contain it for the insoluble or alkali slightly solubility of alkali, and resin that contains the acid dissociation group and radiation-sensitive acid that the effect by acid becomes the alkali ease of solubility produce the radiation-sensitive resin composition of agent,
The above-mentioned resin that contains the acid dissociation group is characterised in that: contain the repetitive of following formula (1) expression, the ratio (Mw/Mn) of weight-average molecular weight (being designated hereinafter simply as Mw) and number-average molecular weight (being designated hereinafter simply as Mn) is less than 1.5.
Mw among the present invention and Mn are respectively to be standard specimen with the polystyrene, the mean molecular weight of measuring and converting by gel permeation chromatography (GPC).
Figure G2003801077532D00031
In the formula (1), R 1Represent hydrogen, methyl, trifluoromethyl or methylol independently of each other, R 2Represent that independently of each other carbon number is that 4～20 1 valency alicyclic hydrocarbon radical or derivatives thereof or carbon number are 1～4 straight or branched alkyl, and R 2At least one be this alicyclic hydrocarbon radical or derivatives thereof, or any 2 R 2Mutually combine, forming the carbon atom comprise combination separately is 4～20 divalent alicyclic hydrocarbon radical or derivatives thereof at interior carbon number, remaining R 2Be that the alkyl of 1～4 straight or branched or carbon number are 4～20 1 valency alicyclic hydrocarbon radical or derivatives thereof for carbon number.
And the above-mentioned resin that contains the acid dissociation group is characterised in that the polymkeric substance that it is to use the active free radical polymerization initiating agent to obtain.
And the above-mentioned resin that contains the acid dissociation group is characterised in that it is the polymkeric substance that constitutes each repetitive atactic polymerization of this resin.
When in the research lithography, producing the reason of tiny flaw, find that group deviation in the substrate manufacturing is with relevant by the variation size of the molecular weight distribution of the resin that contains the acid dissociation group.That is, known that molecular weight distribution must be little.And the formation resist is that the resinous principle of radiation-sensitive resin composition is also clear to the dissolubility reason of propylene glycol methyl ether acetate equal solvent.The present invention is based on that these knowledge finish.
The present invention is by using the active free radical polymerization initiating agent, and the value that can make Mw/Mn can make the variation of the molecular resin amount distribution that contains the acid dissociation group very little less than 1.5 thus.And the resin that contains the acid dissociation group is that atactic polymers can improve the dissolubility to solvent.
Such result is that radiation-sensitive resin composition conduct of the present invention is to active radioactive ray, particularly ArF excimer laser (wavelength 193nm) is the chemically amplified corrosion-resisitng agent of the far ultraviolet induction of representative, not only the transparency to radioactive ray is high, have susceptibility, resolution, anti-dry corrosion, key property that pattern form is good as resist, and first, dissolubility to solvent against corrosion is high, and second can reduce the roughness of the back pattern sidewalls of developing.
Embodiment
When in the research lithography, producing the reason of tiny flaw, find that group deviation in the substrate manufacturing is with relevant by the variation size of the molecular weight distribution of the resin that contains the acid dissociation group.Known that promptly molecular weight distribution must be little.And the formation resist is that the resinous principle of radiation-sensitive resin composition is also clear to the dissolubility reason of propylene glycol methyl ether acetate equal solvent.The present invention is based on that these knowledge finish.
Can enumerate (methyl) acrylate of formula (1-1) expression as the monomer of the repetitive of production (1) expression.
Figure G2003801077532D00041
In the following formula (1-1), R 1And R 2Respectively and the R in the formula (1) 1And R 2Identical.
As R 2In carbon number be that 4～20 1 valency alicyclic hydrocarbon radical or derivatives thereof or at least one are the alicyclic hydrocarbon radical or derivatives thereof, perhaps any 2 R 2Mutually combine, the carbon atom that comprises combination separately, can be enumerated and for example serve as reasons from dicyclo [2.2.1] heptane, three ring [5.2.1.0 for carbon number is 4～20 divalent alicyclic hydrocarbon radical or derivatives thereof interior 2,6] decane, Fourth Ring [6.2.1.1 3,6.0 2,7] group that constitutes of the alicyclic ring of loop chain alkanes such as dodecane, diamantane, cyclopentane, cyclohexane etc.; The group that these alicyclic rings constitute with for example carbon numbers such as methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, 2-methyl-propyl, 1-methyl-propyl, the tert-butyl group be 1～4 straight chain, side chain or ring-type alkyl more than a kind or the group that replaces more than 1 etc.
And, as R 21 valency or the derivant of divalent alicyclic hydrocarbon radical can enumerate and have more than a kind or the hydroxyl for example of the substituting group more than 1; Carboxyl; The oxo base (promptly=the O yl); Carbon numbers such as methylol, 1-hydroxyethyl, 2-hydroxyethyl, 1-hydroxypropyl, 2-hydroxypropyl, 3-hydroxypropyl, 2-hydroxyl butyl, 3-hydroxyl butyl, 4-hydroxyl butyl are 1～4 hydroxyalkyl; Carbon numbers such as methoxyl, ethoxy, positive propoxy, isopropoxy, n-butoxy, 2-methyl propoxyl group, 1-methyl propoxyl group, tert-butoxy are 1～4 alkoxy; Cyano group; Carbon numbers such as cyanogen methyl, 2-cyanogen methyl, 3-cyanogen propyl group, 4-cyanogen butyl are the group of cyanoalkyl of 2～5 etc.In these substituting groups, preferred hydroxyl, carboxyl, methylol, cyano group, cyanogen methyl etc.
And, as R 2Carbon number be that the alkyl of 1～4 straight or branched can have been enumerated for example methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, 2-methyl-propyl, 1-methyl-propyl, the tert-butyl group etc.Preferable methyl, ethyl, n-pro-pyl, isopropyl in these alkyl.
As forming in the formula (1)-C (R 2) 3Functional group's side chain, preferred example can have been enumerated 1-methyl isophthalic acid-cyclopentyl, 1-ethyl-1-cyclopentyl, 1-methyl isophthalic acid-cyclohexyl, 1-ethyl-1-cyclohexyl, 2-methyl adamantane-2-base, 2-methyl-3-hydroxyadamantane-2-base, 2-ethyl diamantane-2-base, 2-ethyl-3-hydroxyadamantane-2-base, 2-n-pro-pyl diamantane-2-base, 2-n-pro-pyl-3-hydroxyadamantane-2-base, 2-isopropyl diamantane-2-base, 2-isopropyl-3-hydroxyadamantane-2-base, 2-methyl bicycle [2.2.1] heptan-2-base, 2-ethyl dicyclo [2.2.1] heptan-2-base, 8-methyl three ring [5.2.1.0 2,6] last of the ten Heavenly stems-8-base, 8-ethyl tricyclo [5.2.1.0 2,6] last of the ten Heavenly stems-8-base, 4-methyl-Fourth Ring [6.2.1.1 3,6.0 2,7] 12-4-base, 4-ethyl-Fourth Ring [6.2.1.1 3,6.0 2,7] 12-4-base, 1-(dicyclo [2.2.1] heptan-2-yl)-1-Methylethyl, 1-(three ring [5.2.1.0 2,6] last of the ten Heavenly stems-the 8-yl)-1-Methylethyl, 1-(Fourth Ring [6.2.1.1 3,6.0 2,7] 12-4-yl)-1-Methylethyl, 1-(diamantane-1-yl)-1-Methylethyl, 1-(3-hydroxyadamantane-1-yl)-1-Methylethyl, 1,1-dicyclohexyl ethyl, 1,1-two (dicyclo [2.2.1] heptan-2-yl) ethyl, 1,1-two (three ring [5.2.1.0 2,6] last of the ten Heavenly stems-the 8-yl) ethyl, 1,1-two (Fourth Ring [6.2.1.1 3,6.0 2,7] 12-4-yl) ethyl, 1,1-two (diamantane-1-yl) ethyl etc.
And, enumerate the example that is fit in the monomer of repetitive of giving construction (1-1) expression below.
Can enumerate (methyl) acrylic acid 1-methyl isophthalic acid-ring pentyl ester, (methyl) acrylic acid 1-ethyl-1-encircles pentyl ester, (methyl) acrylic acid 1-methyl isophthalic acid-cyclohexyl, (methyl) acrylic acid 1-ethyl-1-cyclohexyl, (methyl) acrylic acid 2-methyl adamantane-2-base ester, (methyl) acrylic acid 2-methyl 3-hydroxyadamantane-2-base ester, (methyl) acrylic acid 2-ethyl diamantane-2-base ester, (methyl) acrylic acid 2-ethyl 3-hydroxyadamantane-2-base ester, (methyl) acrylic acid 2-n-pro-pyl-diamantane-2-base ester, (methyl) acrylic acid 2-n-pro-pyl 3-hydroxyadamantane-2-base ester, (methyl) acrylic acid 2-isopropyl diamantane-2-base ester, (methyl) acrylic acid 2-isopropyl 3-hydroxyadamantane-2-base ester, (methyl) acrylic acid 2-methyl adamantane-2-base ester, (methyl) acrylic acid 2-methyl bicycle [2.2.1] heptan-2-base ester, (methyl) acrylic acid 2-ethyl dicyclo [2.2.1] heptan-2-base ester, (methyl) acrylic acid 8-methyl three ring [5.2.1.0 2,6] last of the ten Heavenly stems-8-base ester, (methyl) acrylic acid 8-ethyl tricyclo [5.2.1.0 2,6] last of the ten Heavenly stems-8-base ester, (methyl) acrylic acid 4-methyl Fourth Ring [6.2.1.1 3,6.0 2,7] 12-4-base ester, (methyl) acrylic acid 4-ethyl Fourth Ring [6.2.1.1 3,6.0 2,7] 12-4-base ester, (methyl) acrylic acid 1-(dicyclo [2.2.1] heptan-2-yl)-1-methyl esters, (methyl) acrylic acid 1-(three ring [5.2.1.0 2,6] last of the ten Heavenly stems-the 8-yl)-1-methyl esters, (methyl) acrylic acid 1-(Fourth Ring [6.2.1.1 3,6.0 2,7] 12-4-yl)-1-Methylethyl ester, (methyl) acrylic acid 1-(diamantane-1-yl)-1-Methylethyl ester, (methyl) acrylic acid 1-(3-hydroxyadamantane-1-yl)-1-Methylethyl ester, (methyl) acrylic acid 1,1-dicyclohexyl ethyl ester, (methyl) acrylic acid 1,1-two (dicyclo [2.2.1] heptan-2-yl) ethyl ester, (methyl) acrylic acid 1,1-two (three ring [5.2.1.0 2,6] last of the ten Heavenly stems-the 8-yl) ethyl ester, (methyl) acrylic acid 1,1-two (Fourth Ring [6.2.1.1 3,6.0 2,7] 12-4-yl) ethyl ester, (methyl) acrylic acid 1,1-two (diamantane-1-yl) ethyl ester.
As particularly suitable monomer in the monomer of the repetitive that gives following formula (1-1) expression, can enumerate (methyl) acrylic acid 1-methyl isophthalic acid-ring pentyl ester, (methyl) acrylic acid 1-ethyl-1-encircles pentyl ester, (methyl) acrylic acid 1-methyl isophthalic acid-cyclohexyl, (methyl) acrylic acid 1-ethyl-1-cyclohexyl, (methyl) acrylic acid 2-methyl adamantane-2-base ester, (methyl) acrylic acid 2-ethyl diamantane-2-base ester, (methyl) acrylic acid 2-n-pro-pyl diamantane-2-base ester, (methyl) acrylic acid 2-isopropyl diamantane-2-base ester, (methyl) acrylic acid 1-(diamantane-1-yl)-1-Methylethyl ester.These monomers can use or mix use separately.
Mw/Mn involved in the present invention preferably contains the repetitive of formula (1) expression and the repetitive more than at least 1 of the repetitive that is selected from following formula (2)～formula (7) expression less than 1.5 the resin that contains the acid dissociation group.
In following formula (2)～(7), R 1And the R in the formula (1) 1Identical.
In the formula (2), A represents the alkylidene that can have substituent straight or branched, list or two alkylene glycol-based, the alkylene ester group of singly-bound or 1～6 carbon atom, and what B represented singly-bound or 1～3 carbon atom can have substituent alkylidene, alkoxy, oxygen atom.
In the formula (3), E represents that singly-bound or carbon number are 1～3 divalent alkyl, R 3Represent independently of each other hydroxyl, cyano group, carboxyl ,-COOR 5Or-Y-R 6, R 5Be that the alkyl of 1～4 straight or branched or carbon number are 3～20 alicyclic alkyl for hydrogen atom or carbon number, Y represents that independently of each other singly-bound or carbon number are 1～3 divalent alkylidene, R 6Represent independently of each other hydrogen atom, hydroxyl, cyano group or-COOR 7At least one R but 3It or not hydrogen atom.E and Y can enumerate singly-bound, methylene, ethylidene, propylidene.
And, as-COOR 7In R 7Expression hydrogen atom or carbon number are that the alkyl of 1～4 straight or branched or carbon number are 3～20 alicyclic alkyl.The alkyl that as carbon number is 1～4 straight or branched can have methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, 2-methyl-propyl, 1-methyl-propyl, the tert-butyl group for example.Being 3～20 alicyclic alkyl as carbon number is-C nH 2n-1The naphthenic base of (n is 3～20 integer) expression, for example cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, suberyl, ring octyl group etc., and how ring-like alicyclic alkyl, for example dicyclo [2.2.1] heptyl, three ring [5.2.1.0 2,6] decyl, Fourth Ring [6.2.1.1 3,6.0 2,7] dodecyl, adamantyl etc., and with straight chain, side chain or cyclic alkyl more than a kind or the group of 1 an above substituted cycloalkyl or a how ring-like alicyclic alkyl part etc.
In the formula (4), G represents that singly-bound, carbon number are that the alkylidene of 1～6 straight or branched or carbon number are 4～20 divalent alicyclic hydrocarbon radical, alkylene glycol base, alkylene ester group.The alkylene base that as carbon number is 1～6 straight or branched can have been enumerated methylene base, ethylene group, trimethylene base, fourth support base, pentamethylene base, hexamethylene base, cyclohexalene base etc.
In the formula (5), J represents that singly-bound, carbon number are 1～20 the alkylidene that substituent straight chain, side chain, ring-type can be arranged, alkylene glycol base, alkylene ester group.
In the formula (6), L represent singly-bound, carbon number be 1～20 substituent straight chain, side chain, ring-type alkylene base, alkylene glycol base, alkylene ester group, R can be arranged 4Expression hydrogen atom, carbon number are that alkyl, alkoxy, hydroxyalkyl, the carbon number of 1～4 straight or branched is the alicyclic hydrocarbon radical of 3～20 divalent or the group that forms its derivant.Q is 1 or 2.
In the formula (7), N, M represent the alkylene base that can have substituent straight chain, side chain, ring-type, alkylene glycol base, the alkylene ester group of singly-bound, 1～20 carbon atom respectively independently.Methylene base, ethylene group, trimethylene base, fourth support base, pentamethylene base, hexamethylene base, cyclohexalene base etc. can have been enumerated as the alkylene base of straight or branched.P is 0 or 1.
Can enumerate the compound of formula (2-1) expression as the monomer of the repetitive of production (2) expression.
R in the formula (2-1) 1Expression hydrogen atom or methyl, A and B are identical with A and B in the formula (2).In addition, be that the alkylene base of 1～6 straight or branched can have been enumerated methylene base, ethylene group, trimethylene base, fourth support base, pentamethylene base, hexamethylene base, cyclohexalene base as carbon number among the A.
Can enumerate the monomer of following formula (2-1-1)～(2-1-7) expression as preferred monomer in the monomer of formula (2-1) expression.
Here R 1Any for hydrogen atom, methyl, trifluoromethyl, methylol, and the monomer that replaces above-mentioned methylene base to obtain with oxygen atom on 7 of norbornane end of the bridge illustrates for example as preferred monomer.
Can enumerate the compound of formula (3-1) expression as the monomer of the repetitive of production (3) expression.
Figure G2003801077532D00101
In the formula (3-1), R 1Expression hydrogen atom or methyl, E and R 3And E and R in the formula (3) 3Identical.
Preferred monomers in the monomer of following enumerative (3-1) expression.
(methyl) acrylic acid 3-hydroxyadamantane ester, (methyl) acrylic acid 3-hydroxyadamantane-1-base methyl esters, (methyl) acrylic acid 3,5-dihydroxy diamantane-1-base methyl esters, (methyl) acrylic acid 3-hydroxyl-5-Cyanoadamantyl-1-base methyl esters, (methyl) acrylic acid 3-hydroxyl-5-carboxyl diamantane-1-base methyl esters, (methyl) acrylic acid 3-hydroxy-5-methyl oxygen base carbonyl diamantane-1-base methyl esters, (methyl) acrylic acid 3-hydroxymethyl diamantane-1-base methyl esters, (methyl) acrylic acid 3,5-dihydroxymethyl diamantane-1-base methyl esters, (methyl) acrylic acid 3-hydroxyl-5-methylol diamantane-1-base methyl esters, (methyl) acrylic acid 3-cyano group-5-methylol diamantane-1-base methyl esters, (methyl) acrylic acid 3-methylol-5-carboxyl diamantane-1-base methyl esters, (methyl) acrylic acid 3-methylol-5-methoxycarbonyl group diamantane-1-base methyl esters, (methyl) acrylic acid 3-Cyanoadamantyl-1-base methyl esters, (methyl) acrylic acid 3,5-dicyano diamantane-1-base methyl esters, (methyl) acrylic acid 3-cyano group-5-carboxyl diamantane-1-base methyl esters, (methyl) acrylic acid 3-cyano group-5-methoxycarbonyl group diamantane-1-base methyl esters, (methyl) acrylic acid 3-carboxyl diamantane-1-base methyl esters, (methyl) acrylic acid 3, the basic methyl esters of 5-dicarboxyl diamantane-1, (methyl) acrylic acid 3-carboxyl-5-methoxycarbonyl group diamantane-1-base methyl esters, (methyl) acrylic acid 3-methoxycarbonyl group diamantane-1-base methyl esters, (methyl) acrylic acid 3,5-dimethoxycarbonyl diamantane-1-base methyl esters;
(methyl) acrylic acid 3-hydroxy-5-methyl base diamantane-1-base ester, (methyl) acrylic acid 3,5-dihydroxy-7-methyl adamantane-1-base ester, (methyl) acrylic acid 3-hydroxyl-5-cyano group-7-methyl adamantane-1-base ester, (methyl) acrylic acid 3-hydroxyl-5-carboxyl-7-methyl adamantane-1-base ester, (methyl) acrylic acid 3-hydroxy-5-methyl oxygen carbonyl-7-methyl adamantane-1-base ester, (methyl) acrylic acid 3-methylol-5-methyl adamantane-1-base ester, (methyl) acrylic acid 3,5-dihydroxymethyl-7-methyl adamantane-1-base ester, (methyl) acrylic acid 3-hydroxyl-5-methylol-7-methyl adamantane-1-base ester, (methyl) acrylic acid 3-cyano group-5-methylol-7-methyl adamantane-1-base ester, (methyl) acrylic acid 3-methylol-5-carboxyl-7-methyl adamantane-1-base ester, (methyl) acrylic acid 3-methylol-5-methoxycarbonyl group-7-methyl adamantane-1-base ester, (methyl) acrylic acid 3-cyano group-5-methyl adamantane-1-base ester, (methyl) acrylic acid 3,5-dicyano-7-methyl adamantane-1-base ester, (methyl) acrylic acid 3-cyano group-5-carboxyl-7-methyl adamantane-1-base ester, (methyl) acrylic acid 3-cyano group-5-methoxycarbonyl group-7-methyl adamantane-1-base ester, (methyl) acrylic acid 3-carboxyl-5-methyl adamantane-1-base ester, (methyl) acrylic acid 3,5-dicarboxyl-7-methyl adamantane-1-base ester, (methyl) acrylic acid 3-carboxyl-5-methoxycarbonyl group-7-methyl adamantane-1-base ester, (methyl) acrylic acid 3-methoxycarbonyl group-5-methyl adamantane-1-base ester, (methyl) acrylic acid 3,5-dimethoxycarbonyl-7-methyl adamantane-1-base ester;
(methyl) acrylic acid 3-hydroxy-5-methyl base diamantane-1-base methyl esters, (methyl) acrylic acid 3,5-dihydroxy-7-methyl adamantane-1-base methyl esters, (methyl) acrylic acid 3-hydroxyl-5-cyano group-7-methyl adamantane-1-base methyl esters, (methyl) acrylic acid 3-hydroxyl-5-carboxyl-7-methyl adamantane-1-base methyl esters, (methyl) acrylic acid 3-hydroxy-5-methyl oxygen carbonyl-7-methyl adamantane-1-base methyl esters, (methyl) acrylic acid 3-methylol-5-methyl adamantane-1-base methyl esters, (methyl) acrylic acid 3,5-dihydroxymethyl-7-methyl adamantane-1-base methyl esters, (methyl) acrylic acid 3-hydroxyl-5-methylol-7-methyl adamantane-1-base methyl esters, (methyl) acrylic acid 3-cyano group-5-methylol-7-methyl adamantane-1-base methyl esters, (methyl) acrylic acid 3-methylol-5-carboxyl-7-methyl adamantane-1-base methyl esters, (methyl) acrylic acid 3-methylol-5-methoxycarbonyl group-7-methyl adamantane-1-base methyl esters, (methyl) acrylic acid 3-cyano group-5-methyl adamantane-1-base methyl esters, (methyl) acrylic acid 3,5-dicyano-7-methyl adamantane-1-base methyl esters, (methyl) acrylic acid 3-cyano group-5-carboxyl-7-methyl adamantane-1-base methyl esters, (methyl) acrylic acid 3-cyano group-5-methoxycarbonyl group-7-methyl adamantane-1-base methyl esters, (methyl) acrylic acid 3-carboxyl-5-methyl adamantane-1-base methyl esters, (methyl) acrylic acid 3,5-dicarboxyl-7-methyl adamantane-1-base methyl esters, (methyl) acrylic acid 3-carboxyl-5-methoxycarbonyl group-7-methyl adamantane-1-base methyl esters, (methyl) acrylic acid 3-methoxycarbonyl group-5-methyl adamantane-1-base methyl esters, (methyl) acrylic acid 3,5-dimethoxycarbonyl-7-methyl adamantane-1-base methyl esters;
(methyl) acrylic acid 3-hydroxyl-5,7-dimethyladamantane-1-base ester, (methyl) acrylic acid 3-methylol-5,7-dimethyladamantane-1-base ester, (methyl) acrylic acid 3-cyano group-5,7-dimethyladamantane-1-base ester, (methyl) acrylic acid 3-carboxyl-5,7-dimethyladamantane-1-base ester, (methyl) acrylic acid 3-methoxycarbonyl group-5,7-dimethyladamantane-1-base ester, (methyl) acrylic acid 3-hydroxyl-5,7-dimethyladamantane-1-base methyl esters, (methyl) acrylic acid 3-methylol-5,7-dimethyladamantane-1-base methyl esters, (methyl) acrylic acid 3-cyano group-5,7-dimethyladamantane-1-base methyl esters, (methyl) acrylic acid 3-carboxyl-5,7-dimethyladamantane-1-base methyl esters, (methyl) acrylic acid 3-methoxycarbonyl group-5,7-dimethyladamantane-1-base methyl esters etc.
Particularly preferred monomer can have been enumerated (methyl) acrylic acid 3-hydroxyadamantane-1-base ester in the monomer of formula (3-1) expression, (methyl) acrylic acid 3-hydroxyadamantane-1-base methyl esters, (methyl) acrylic acid 3,5-dihydroxy diamantane-1-base methyl esters, (methyl) acrylic acid 3-Cyanoadamantyl-1-base methyl esters, (methyl) acrylic acid 3-carboxyl diamantane-1-base methyl esters, (methyl) acrylic acid 3-hydroxy-5-methyl base diamantane-1-base ester, (methyl) acrylic acid 3,5-dihydroxy-7-methyl adamantane-1-base ester, (methyl) acrylic acid 3-hydroxyl-5,7-dimethyladamantane-1-base ester, (methyl) acrylic acid 3-carboxyl-5,7-dimethyladamantane-1-base ester, (methyl) acrylic acid 3-hydroxyl-5,7-dimethyladamantane-1-base methyl esters etc.
Can enumerate the compound of formula (4-1) expression as the monomer of the repetitive of production (4) expression.
In the formula (4-1), R 1Expression hydrogen atom, methyl, trifluoromethyl or methylol, G is identical with G in the formula (4).
In the monomer of formula (4-1) expression, particularly preferred monomer can be enumerated the monomer of following formula (4-1-1)～formula (4-1-8) expression.
In the following formula, R 1Any for hydrogen atom, methyl, trifluoromethyl or methylol, and the preferred monomer that on 7 of norbornane end of the bridge, replaces above-mentioned methylene base to obtain with oxygen atom.
Can enumerate the compound of formula (5-1) expression as the monomer of the repetitive of production (5) expression.
Figure G2003801077532D00141
In the formula (5-1), R 1Expression hydrogen atom or methyl, J is identical with J in the formula (5).
In the monomer of formula (5-1) expression, particularly preferred monomer can be enumerated the monomer of following formula (5-1-1)～formula (5-1-4) expression.
In the following formula, R 1Any for hydrogen atom, methyl, trifluoromethyl or methylol.
Can enumerate the compound of formula (6-1) expression as the monomer of the repetitive of production (6) expression.
Figure G2003801077532D00151
In the formula (6-1), R 1Expression hydrogen atom, methyl, trifluoromethyl or methylol, q, L and R 4And q, L and R in the formula (6) 4Identical.
In the monomer of expression, particularly preferred monomer can be enumerated the monomer of following formula (6-1-1)～formula (6-1-15) expression in the formula (6-1).
In the following formula, as R 4Preferred example hydrogen atom, methyl, ethyl, propyl group, butyl, cyclohexyl, norborneol alkyl, adamantyl, methoxyl, ethoxy, propoxyl group, butoxy, methylol, hydroxyethyl etc. are arranged.
Can enumerate the compound of formula (7-1) expression as the monomer of the repetitive of production (7) expression.
In the formula (7-1), R 1Expression hydrogen atom, methyl, trifluoromethyl or methylol, N, M and p are identical with N, M and p in the formula (7).
In the monomer of formula (7-1) expression, particularly preferred monomer can be enumerated the monomer of following formula (7-1-1)～formula (7-1-9) expression.
Figure G2003801077532D00181
Mw/Mn involved in the present invention can further contain repetitive other repetitives in addition of formula (1)～formula (7) expression less than 1.5 the resin that contains the acid dissociation group.
As the monomer that generates other repetitives for example can enumerate (methyl) acrylic acid hydroxyl methyl esters, 1-(methyl) acrylic acid-2-hydroxyl methyl esters, (methyl) acrylic acid, (methyl) acrylic acid-5 (6)-hydroxyl dicyclo [2.2.1] heptan-2-base ester, (methyl) acrylic acid-9 (10)-hydroxyl Fourth Ring [6.2.1.1 3,6.0 2,7] 12-4-base ester, (methyl) acrylic acid carboxyl ester, (methyl) acrylic acid-2-carboxyl ethyl ester, (methyl) acrylic acid-3-carboxyl diamantane-1-base ester, (methyl) acrylic acid-5 (6)-carboxyl dicyclo [2.2.1] heptan-2-base ester, (methyl) acrylic acid-9 (10)-carboxyl Fourth Ring [6.2.1.1 3,6.0 2,7] 12-4-base ester, (methyl) acrylic acid cyano group methyl esters, 1-(methyl) 2-cyanoethyl acrylate, (methyl) acrylic acid-3-Cyanoadamantyl-1-base ester, (methyl) acrylic acid-5 (6)-cyano-bicyclo [2.2.1] heptan-2-base ester, (methyl) acrylic acid-9 (10)-cyano group Fourth Ring [6.2.1.1 3,6.0 2,7] 12-4-base ester, (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) acrylic acid diamantane-1-base ester, (methyl) acrylic acid dicyclo [2.2.1] heptan-2-base ester, (methyl) acrylic acid-7,7-dimethyl dicyclo [2.2.1] heptan-1-base ester, (methyl) acrylic acid three ring [5.2.1.0 2,6] last of the ten Heavenly stems-8-base ester;
(methyl) acrylic acid-7-oxo-6-oxidation dicyclo [3.2.1] suffering-4-base ester, (methyl) acrylic acid-2-methoxycarbonyl group-7-oxo-6-oxidation dicyclo [3.2.1] suffering-4-base ester, (methyl) acrylic acid-2-oxo tetrahydropyran-4-base ester, (methyl) acrylic acid-4-methyl-2-oxo tetrahydropyran-4-base ester, (methyl) acrylic acid-5-oxo-tetrahydrofuran-3-base ester, (methyl) acrylic acid-2,2-dimethyl-5-oxo-tetrahydrofuran-3-base ester, (methyl) acrylic acid-4,4-dimethyl-5-oxo-tetrahydrofuran-3-base ester, (methyl) acrylic acid-2-oxo-tetrahydrofuran-3-base ester, (methyl) acrylic acid-4,4-dimethyl-2-oxo-tetrahydrofuran-3-base ester, (methyl) acrylic acid-5,5-dimethyl-2-oxo-tetrahydrofuran-3-base ester, (methyl) acrylic acid-5-oxo-tetrahydrofuran-2-base methyl esters, (methyl) acrylic acid-3,3-dimethyl-5-oxo-tetrahydrofuran-2-base methyl esters, N, N-dimethyl (methyl) acrylamide, crotonamide, maleic amide, fumaramide, methyl corydalis tuber acid amides, citraconoyl amine, clothing health acid amides etc.; Methylene glycol two (methyl) acrylate, ethylene glycol bisthioglycolate (methyl) acrylate, 2,5-dimethyl-2,5-hexanediol two (methyl) acrylate, 1,2-diamantane glycol two (methyl) acrylate, 1,3-diamantane glycol two (methyl) acrylate, 1,4-diamantane glycol two (methyl) acrylate, three ring decyl dihydroxymethyl two (methyl) acrylate etc.
Mw/Mn involved in the present invention preferably is made of at least a repetitive of the repetitive of the repetitive of formula (1) expression and formula (2)～formula (7) expression less than 1.5 the resin that contains the acid dissociation group.
The ratio of repetitive (1) in multipolymer is 15～70 moles of % with respect to whole repetitives, is preferably 15～25 moles of %.Less than 15 moles of %, as the resolution of resist the trend of variation is arranged, surpass 70 moles of %, the trend of reduction is arranged as the development of resist.
Have in multipolymer under the situation of repetitive (2), repetitive (2) is 5～70 moles of % with respect to the ratio of whole repetitives, is preferably 5～60 moles of %;
Have in multipolymer under the situation of repetitive (3), repetitive (3) is 5～70 moles of % with respect to the ratio of whole repetitives, is preferably 5～50 moles of %;
Have in multipolymer under the situation of repetitive (4), repetitive (4) is 5～70 moles of % with respect to the ratio of whole repetitives, is preferably 5～50 moles of %;
Have in multipolymer under the situation of repetitive (5), repetitive (5) is 5～70 moles of % with respect to the ratio of whole repetitives, is preferably 5～50 moles of %;
Have in multipolymer under the situation of repetitive (6), repetitive (6) is 5～70 moles of % with respect to the ratio of whole repetitives, is preferably 5～50 moles of %;
Have in multipolymer under the situation of repetitive (7), repetitive (7) is 5～70 moles of % with respect to the ratio of whole repetitives, is preferably 5～50 moles of %.
The containing ratio of repetitive (2) surpasses 70 moles of %, has the trend that resolution variation and the dissolubility in the resist solvent reduce.The containing ratio of repetitive (3) surpasses 70 moles of %, and development has the trend of reduction.The containing ratio of repetitive (4) surpasses 70 moles of %, and anti-dry corrosion has the trend of reduction.The containing ratio of repetitive (5) surpasses 70 moles of %, and resolution has the trend of reduction.The containing ratio of repetitive (6) surpasses 70 moles of %, and development has the trend of reduction.The containing ratio of repetitive (7) surpasses 70 moles of %, and development has the trend of reduction.
The resin that contains the acid dissociation group can easily make the value of its Mw/Mn less than 1.5 by the active free radical polymerization that uses the active free radical polymerization initiating agent.
As the active free radical polymerization that uses among the present invention, the meaning is to keep the free radical polymerization that the activity of polymerization end is not lost.The living polymerization of narrow sense is meant the terminal active polymerization that always keeps, and comprises also that generally end has the plan living polymerization that does not activate with the equilibrium state of activate.Definition among the present invention also comprises the latter.There are many research groups that active free radical polymerization is being carried out positive research in recent years.Its example can be enumerated and use chain-transferring agents such as polysulfide, use Cobalt Porphyrin chelate (J.Am.Chem.Soc.1994,116,7943) and (Macromolecules of free radical scavenger such as nitroxide compound, 1994,27,7228), make initiating agent with organic halogen compound etc., do with transition metal complex catalyzer atomic migration free radical polymerization (spy opens 2002-145972, the spy opens 2002-80523, the spy opens 2001-261733, the spy opens 2000-264914), at the terminal (WO9801478A1 of growth with RCSS, WO9858974A1, WO9935177A1, WO9931144, US6380335B1) etc.
Below, the active free radical polymerization system that is fit among the present invention is described.
At the active free radical polymerization that is used for preparing the resin that contains the acid dissociation group, at first illustrate in initiating agent in the example that uses hot radical to produce agent and nitroxide compound, about the method for the free radical scavenger of the nitroxide compound that uses the active free radical polymerization initiating agent.In this polymerization general use stable nitroxid (=N-O) as free radical scavenger.As such compound without limits, but preferred 2,2,6,6-replacement-1-piperidines oxygen radical and 2,2,5,5-replacement-1-piperidines oxygen radical etc., from the nitroxid of cyclic hydroxylamine.As substituting group, carbon numbers such as methyl and ethyl are suitable at the alkyl below 4.
As concrete nitroxid compound without limits, still can enumerate 2,2,6,6-tetramethyl-1-piperidines oxygen radical (TEMPO), 2,2,6,6-tetraethyl-1-piperidines oxygen radical, 2,2,6,6-tetramethyl-4-oxo-1-piperidines oxygen radical, 2,2,5,5-tetramethyl-1-pyrrolidine oxygen radical, 1,1,3,3-tetramethyl-2-iso-indoles oxygen radical, N, N-two tert-butylamine oxygen radicals etc.Also can use stable free radicals such as galvinoxyl free radical to replace nitroxid.
Above-mentioned free radical scavenger can produce agent with hot radical and be used in combination.The reaction product of free radical scavenger and hot radical generation agent thinks to carry out the polymerization initiator of addition polymerization monomer polymerization.The ratio that both are used in combination is not particularly limited, but the free radical scavenger with respect to 1 mole, and it is suitable that hot radical generation agent is 0.1～10 mole.
Produce agent as hot radical and can use all cpds, but preferably can under the temperature conditions of polymerization, produce the superoxide and the azo-compound of free radical.As this superoxide without limits, diacyl peroxide classes such as benzoyl peroxide, lauroyl peroxide are arranged; Dialkyl peroxide such as cumyl peroxide, di-t-butyl peroxide class; Peroxycarbonates classes such as diisopropyl peroxydicarbonate, two (4-tert-butylcyclohexyl) peroxy dicarbonate; Alkyl peroxyesters such as tert-butyl hydroperoxide caprylate, tert butyl peroxy benzoate etc.Preferred especially benzoyl peroxide.Can enumerate 2 as azo-compound, 2 '-azoisobutyronitrile, 2,2 '-azo two-(2, the 4-methyl pentane nitrile), 2,2 '-azo two-(4-methoxyl-2,4-methyl pentane nitrile), azo-bis-iso-dimethyl etc., preferred especially azo-bis-iso-dimethyl.
And, in Macromolecules, nineteen ninety-five the 28th are rolled up the 2993rd page, putting down in writing, can use the alkoxyamine compounds of formula (9) and formula (10) expression to replace hot radical generation agent and free radical scavenger as initiating agent.
Use under the situation of alkoxyamine compound as initiating agent, the compound with functional group such as hydroxyl of use formula (10) expression can be had the polymkeric substance of functional group endways.
State polymerizing conditions such as monomer used in the polymerization of free radical scavengers such as nitroxide compound, solvent, polymerization temperature in the use without limits, identically with the condition of using in the atomic migration free radical polymerization that the following describes also have no relations.
As the active free radical polymerization initiating agent, the polymerization initiator that can use transition metal complex compound and organohalogen compounds, lewis acid or amine to constitute.
Preferably enumerate the element (compiling the periodic table of " chemistry quick checking basis piece of writing I revises the 4th edition " (1993) record according to Japanization association) of periodic table the 7th～11 families such as iron, copper, nickel, rhodium, ruthenium, rhenium as the central metal that constitutes transition metal complex compound.Wherein preferred ruthenium and copper.
Ruthenium is made the object lesson of the transition metal complex compound of central metal can enumerate dichloro three (triphenylphosphine) ruthenium, dichloro three (tributylphosphine) ruthenium, dichloro (cyclo-octadiene) ruthenium, the dichloro-benzenes ruthenium, dichloro is to the cymol ruthenium, dichloro (norbornadiene) ruthenium, suitable-dichloro two (2,2 '-bipyridine) ruthenium, dichloro three (1, the 10-phenanthroline) ruthenium, phosgene hydrogenation three (triphenylphosphine) ruthenium, two (triphenylphosphine) rutheniums of chloro cyclopentadienyl group, two (triphenylphosphine) rutheniums of chloro pentamethyl cyclopentadienyl group, two (triphenylphosphine) rutheniums of chloro indenyl etc., preferred especially dichloro three (triphenylphosphine) ruthenium, two (triphenylphosphine) rutheniums of chloro pentamethyl cyclopentadienyl group or two (triphenylphosphine) rutheniums of chloro indenyl.
Organohalogen compounds have the function of polymerization initiator.Such a organohalogen compounds can use α-Lu Daitangjihuahewu or alpha-halogenated carboxylic acids ester, wherein preferred alpha-halogenated carboxylic acids ester, its object lesson has 2 bromo 2 methyl propionic acid ethyl ester, 2 bromopropionic acid 2-hydroxyl ethyl ester, 2-chloro-2,4,4-trimethyl dimethyl glutarate etc.
Lewis acid or amine have the function of activator.Such a lewis acid for example can have been enumerated tri-alkoxy aluminium such as aluminium isopropoxide and three (tert-butoxy) aluminium; Two (substituted aryloxy) aluminum alkylss such as two (2,6-di-t-butyl phenoxy group) aluminium methyl, two (2,4, the 6-tri-butyl-phenoxy) aluminium methyl; Three (substituted aryloxy) aluminium such as three (2,6-diphenyl phenoxy group) aluminium; Four alkoxytitaniums such as tetraisopropoxy titanium etc. are preferably tri-alkoxy aluminium, preferred especially aluminium isopropoxide.
For example Armeens such as methylamine, ethamine, propylamine, isopropylamine, butylamine can have been enumerated as amine, secondary aliphatic amines such as dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, dibutylamine, fatty amines such as aliphatic tertiary amine such as trimethylamine, triethylamine, tripropyl amine (TPA), tri-isopropyl amine, tri-n-butylamine; N, N, N ', N '-tetramethylethylenediamine, N, N, N ', N ", N "-five methyl diethylentriamine, 1,1,4,7,10, aliphatic polyamines such as 10-hexamethyl trien; Primary aromatic amine such as aniline, toluidine, aromatic amines such as diphenylamine, aromatic amines such as aromatic nitrile bases such as triphenylamine etc.Wherein, preferred aliphat amine, preferred especially butylamine, dibutylamine, tri-n-butylamine etc.
Content ratio for each composition in the polymerization initiator system of transition metal complex compound and organohalogen compounds and lewis acid or amine formation, not to its qualification, but the too low words of ratio with respect to the transition metal complex compound of organohalogen compounds, the polymerization meeting is slack-off, otherwise, the molecular weight distribution of the polymkeric substance that too high words obtain can broaden, thereby the mol ratio of transition metal complex compound and organohalogen compounds is preferably 0.05: 1～1: 1 scope.And, slack-off with respect to the words polymerization meeting that the ratio of the lewis acid of transition metal complex compound or amine is too low, on the contrary the molecular weight distribution of the polymkeric substance that too high words obtain can broaden, thereby the mol ratio of organohalogen compounds and lewis acid or amine is preferably in 1: 1～1: 10 scope.
Above-mentioned active free radical polymerization initiator system can prepare with the polymerization initiator of conventional method hybrid transition metal coordination compound, organohalogen compounds and the activator of lewis acid or amine usually before use.And, preserve transition metal complex compound, polymerization initiator and activator respectively, it is added to respectively in the polymerization reaction system, in polymerization reaction system, mix and obtain also being fine as active free radical polymerization initiator system function.
Can enumerate the compound of formula (8) expression as other active free radical polymerization initiating agent.
Figure G2003801077532D00241
In the formula (8), the carbon number that R ' expression can contain ester group and ether, amino, amide group etc. is 1～15 alkyl or aryl, Y represents singly-bound, oxygen atom, nitrogen-atoms or sulphur atom, R " the expression carbon number that can contain ester group and ether, amino etc. is 1～15 alkyl or aryl.
R ' particularly preferred object lesson when Y is singly-bound can have been enumerated for example methyl, ethyl, propyl group, butyl, cyclohexyl, norborneol alkyl, two norborneol alkyl, adamantyl, phenyl, benzyl, methylol, hydroxyethyl, hydroxy-cyclohexyl etc.
R ' particularly preferred object lesson when Y is oxygen atom can have been enumerated methyl, ethyl, propyl group, butyl, cyclohexyl, norborneol alkyl, two norborneol alkyl, adamantyl, phenyl, benzyl, methylol, hydroxyethyl, hydroxy-cyclohexyl etc.
When Y is nitrogen-atoms, R ' in the following formula (8)-Y-becomes (R ') (R ') N-, and at this moment to have enumerated be methyl, ethyl, propyl group, butyl, cyclohexyl, norborneol alkyl, two norborneol alkyl, adamantyl, phenyl, benzyl, methylol, hydroxyethyl, hydroxy-cyclohexyl, piperidyl, dimethylamino, diethylamino, acetamido etc. to the particularly preferred object lesson of R ' independently.And R ' also can form ring, at this moment is enumerated as the group of formula (8-1)～formula (8-3) expression.
R ' particularly preferred object lesson when Y is sulphur atom can have been enumerated methyl, ethyl, propyl group, butyl, cyclohexyl, norborneol alkyl, two norborneol alkyl, adamantyl, phenyl, benzyl, methylol, hydroxyethyl, hydroxy-cyclohexyl etc.
And, R " particularly preferred object lesson be enumerated as the group of formula (8-4)～formula (8-8) expression.
Figure G2003801077532D00252
Above-mentioned polymerization initiator can be used in combination with the light and heat free-radical generating agent.The object lesson that produces agent as hot radical can enumerate 2,2-azo two (isobutyronotrile), 2,2 '-azo two (2-cyano group-2-butane), dimethyl 2, the two dimethyl isobutyrates of 2 '-azo, 4,4 '-azo two (4-cyanopentanoic acid), 1,1 '-azo two (cyclohexane nitrile), 2-(tert-butyl group azo)-2-dicyanopropane, 2,2 '-azo two [2-methyl-N-(1,1)-and two (methylol)-2-hydroxyethyls] propionamide, 2,2 '-azo two [2-methyl-N-hydroxyethyl]-propionamide, 2,2 '-azo, two (N, N '-two methylene NSC 18620) dihydro chloride, 2,2 '-azo two (2-amidine propane) dihydro chloride, 2,2 '-azo, two (N, N '-two methylene isobutyl amine), 2,2 '-azo two (2-methyl-N-[1, two (the methylol)-2-hydroxyethyls of 1-] propionamide), 2,2 '-azo two (2-methyl-N-[1, two (methylol) ethyls of 1-] propionamide, 2,2 '-azo two [2-methyl-N-(2-hydroxyethyl) propionamide], 2,2-azo two (isobutyl acid amides) dihydrate), 2,2 '-azo two (2,2, the 4-trimethylpentane), 2,2 '-azo (2-methylpropane), the tert-butyl hydroperoxide acetic acid esters, tert butyl peroxy benzoate, the tert-butyl hydroperoxide caprylate, tert-butyl hydroperoxide neodecanoic acid ester, the tert-butyl hydroperoxide isobutyrate, the t-amyl peroxy pivalate, the tert-butyl hydroperoxide pivalate, diisopropyl peroxydicarbonate, peroxidating dicyclohexyl two carbonic esters, cumyl peroxide, dibenzoyl peroxide, dilauroyl peroxide, potassium persulphate, peroxidating two ammonium sulfate, the nitrous acid di tert butyl carbonate, nitrous acid diisopropyl phenyl ester etc.
Can enumerate for example cycloalkane such as cyclohexane, cycloheptane as the solvent that in active free radical polymerization, uses; Saturated carboxylic acid ester classes such as acetic acid ethyl, acetic acid normal-butyl, acetic acid isobutyl, propionic acid methyl, propylene glycol methyl ether acetate; Alkyl lactone classes such as gamma-butyrolacton; Ethers such as tetrahydrofuran, dimethoxy-ethane class, diethoxyethane class etc.; Alkyl ketones such as 2-butanone, 2-heptanone, methyl isobutyl ketone; Naphthenic base ketones such as cyclohexanone; Alcohols such as 2-propyl alcohol, propylene glycol monomethyl ether; The fragrant same clans such as toluene, dimethylbenzene, chlorobenzene; Dimethyl formamide, dimethyl sulfoxide (DMSO), dimethyl acetamide, N-N-methyl-2-2-pyrrolidone N-etc. are non-proton to be polar solvent or solvent-free.
These solvents can separately or mix more than 2 kinds and use.
And the temperature of reaction in the above-mentioned polymerization is generally 40～150 ℃, and preferred 50～130 ℃, the reaction time is generally 1～96 hour, is preferably 1～48 hour.
Its each repetitive that constitutes this resin of the resin that contains the acid dissociation group involved in the present invention does not form block, preferably the polymkeric substance of atactic polymerization.
The monomer methods that constitutes each repetitive as atactic polymerization be by the repetitive that will generate following formula (1)～(7) expression monomer as a whole or mix and drip, polymerization obtains.
Its halogen of the resin that contains the acid dissociation group that obtains, natural the lacking of metal impurities, and the composition of residual monomer and oligomer is below setting, under for example preferred HPLC is 0.1 weight % etc., not only the susceptibility of resist, resolution, processing stability, pattern form etc. can improve further in view of the above, and can obtain impurity and the time-independent resist of susceptibility in the liquid.
The resin that contains the acid dissociation group that obtains under living radical polymerization has end at strand and has situation from the residue of initiating agent.Have this residue do not have yet can not, and then can utilize excessive radical polymerization initiator to remove this residue.The terminal processing is after living free radical polymerization stops, and the end-product of this polyreaction is carried out, and perhaps can carry out the end of polymkeric substance and handle behind the refining polymkeric substance that generates already.
The radical polymerization initiator that can use can use the compound that can produce free radical under molecule chain end base treatment conditions.Generation condition as free radical can have been enumerated high energy radioactive ray such as heat, light, gamma ray or electron beam.
Object lesson as radical polymerization initiator can have been enumerated initiating agents such as superoxide and azo-compound.It has no particular limits, but concrete radical polymerization initiator can have been enumerated tert butyl hydroperoxide, tert butyl peroxy benzoate, benzoyl peroxide, 2,2 '-azo two (2, the 4-methyl pentane nitrile), 2,2 '-azoisobutyronitrile (AIBN), 1,1 '-azo two (cyclohexane nitrile), dimethyl-2,2 '-azo-bis-isobutyrate (MAIB), peace acyloin ether, benzophenone etc.
The temperature of resin terminal groups processing reaction is about 20～200 ℃ when using the hot radical polymerization initiator, preferred 40～150 ℃, and more preferably 50～100 ℃.The atmosphere gas of reaction is inert atmosphere gas or atmospheric atmosphere gas such as nitrogen and argon.The pressure of reaction can be normal pressure or pressurization.The free base unit weight that the amount of radical polymerization initiator produces as radical polymerization initiator, for 1～800% mole of the total mole number of the residue that exists in the polymkeric substance of handling with end is introduced, preferred 50～400% moles, more preferably 100～300% moles, further preferred 200～300% moles.
The terminal reaction time of handling is 0.5～72 hour, preferred 1～24 hour, and more preferably 2～12 hours.At least to remove 50% residues such as thio group from polymer ends, be preferably at least 75%, more preferably 85%, further preferred 95%.The terminal polymkeric substance of handling is for to have new free radical kind endways, and the radical initiator segment that for example is used in the radical initiator generation of using in the terminal processing reaction replaces.The polymkeric substance that obtains has new group endways, can use according to purposes.
In addition, the polymer ends processing also can be to remove the residue that polymerization initiator produces by the method for putting down in writing among the open communique WO02/090397 in the world.
Can enumerate following method about the process for purification that contains the acid dissociation group resin of the present invention.Can enumerate the method for use electro kinetic potential filtrator polymeric adsorbent solution metal and clean resin solution as the method for removing metal impurities, remove the method for the metal that is in the chelate state etc. with acidic aqueous solutions such as oxalic acid and sulfonic acid.And, as levels of residual monomers and oligomer composition being removed liquid extraction method that the method that goes to below the setting has solvent by washing and appropriateness to be used in combination to remove residual monomer and oligomer composition, extracting process for purification such as the ultrafiltration of removing the compound below the specified molecular weight following of solution state and by resin solution being added drop-wise to the reprecipitation method that resin solidified remove residual monomer etc. in poor solvent and being in process for purification under the solid state with resin slurries after the poor solvent cleaning and filtering etc.And these methods can be used in combination.
The poor solvent that uses in above-mentioned reprecipitation method is influenced by the rerum natura of refining resin etc., can not illustrate for example entirely.It is selected that poor solvent can suit.
The Mw that contains the resin of acid dissociation group is the weight-average molecular weight that converts according to gel permeation chromatography (GPC) as standard specimen with polystyrene, and its value is generally 1000～300000, is preferably 2000～200000, more preferably 3000～100000.At this moment, the Mw of resin is less than 1000, and the thermotolerance of resist can reduce, and surpasses 300000 on the other hand, and the development of resist can reduce.
And the ratio (Mw/Mn) of the Mw of resin and Mn is 1～discontented 1.5, be preferably 1～1.3.
Among the present invention, the resin that contains the acid dissociation group can separately or mix more than 2 kinds and use.
In the above-mentioned resin that contains the acid dissociation group, can be by being used in combination the acidic composition of irradiation radioactive ray, promptly radiation-sensitive acid produces agent and obtains radiation-sensitive resin composition.
As radiation-sensitive acid produce the preferred compound of agent be triphenylsulfonium trifluoro-methanyl sulfonate, triphenylsulfonium nine fluorine normal butane sulfonate, triphenylsulfonium perfluor normal octane sulfonate, triphenylsulfonium 2-dicyclo [2.2.1] heptan-2-base-1,1,2,2-HFC-134a sulfonate, triphenylsulfonium 2-(3-Fourth Ring [4.4.0.1 2,5.1 7,10] dodecyl)-1; 1-Difluoroethane sulfonate, triphenylsulfonium N; two (nine fluorine normal butane sulfonyls) the imido hydrochlorates of N-(イ ミ デ-ト), triphenylsulfonium camsilate, 4-cyclohexyl phenyl diphenyl sulfonium trifluoro-methanyl sulfonate, 4-cyclohexyl phenyl diphenyl sulfonium nine fluorine normal butane sulfonate, 4-cyclohexyl phenyl diphenyl sulfonium perfluor normal octane sulfonate, 4-cyclohexyl phenyl diphenyl sulfonium 2-dicyclo [2.2.1] heptan-2-base-1; 1; 2,2-HFC-134a sulfonate, 4-cyclohexyl phenyl diphenyl sulfonium 2-(3-Fourth Ring [4.4.0.1 2,5.1 7,10] dodecyl)-1,1-Difluoroethane sulfonate, 4-cyclohexyl phenyl diphenyl sulfonium N, two (nine fluorine normal butane sulphonyl) the imido hydrochlorates of N-, 4-cyclohexyl phenyl diphenyl sulfonium camsilate,
4-tert-butyl-phenyl diphenyl sulfonium trifluoro-methanyl sulfonate, 4-tert-butyl-phenyl diphenyl sulfonium nine fluorine normal butane sulfonate,
4-tert-butyl-phenyl diphenyl sulfonium perfluor normal octane sulfonate, 4-tert-butyl-phenyl diphenyl sulfonium 2-dicyclo [2.2.1] heptan-2-base-1,1,2,2-HFC-134a sulfonate, 4-tert-butyl-phenyl diphenyl sulfonium 2-(3-Fourth Ring [4.4.0.1 2,5.1 7,10] dodecyl)-1,1-Difluoroethane sulfonate, 4-tert-butyl-phenyl diphenyl sulfonium N, two (nine fluorine normal butane sulfonyls) the imido hydrochlorates of N-, 4-tert-butyl-phenyl diphenyl sulfonium camsilate,
Three (4-tert-butyl-phenyl) sulfonium trifluoro-methanyl sulfonate, three (4-tert-butyl-phenyl) sulfonium, nine fluorine normal butane sulfonate, three (4-tert-butyl-phenyl) sulfonium perfluor normal octane sulfonate, three (4-tert-butyl-phenyl) sulfonium 2-dicyclos [2.2.1] heptan-2-base-1,1,2,2-HFC-134a sulfonate, three (4-tert-butyl-phenyl) sulfonium 2-(3-Fourth Ring [4.4.0.1 2,5.1 7,10] dodecyl)-1,1-Difluoroethane sulfonate, three (4-tert-butyl-phenyl) sulfonium N, two (nine fluorine normal butane sulfonyls) imido hydrochlorate, three (4-tert-butyl-phenyl) the sulfonium camsilates of N-,
Diphenyl iodine trifluoro-methanyl sulfonate, diphenyl iodine nine fluorine normal butane sulfonate, diphenyl iodine perfluor normal octane sulfonate, diphenyl iodine 2-dicyclo [2.2.1] heptan-2-base-1,1,2,2-HFC-134a sulfonate, diphenyl iodine 2-(3-Fourth Ring [4.4.0.1 2,5.1 7,10] dodecyl)-1,1-Difluoroethane sulfonate, diphenyl iodine N, two (nine fluorine normal butane sulfonyls) the imido hydrochlorates of N-, diphenyl iodine camsilate,
Two (4-tert-butyl-phenyl) iodine trifluoro-methanyl sulfonate, two (4-tert-butyl-phenyl) iodine, nine fluorine normal butane sulfonate, two (4-tert-butyl-phenyl) iodine perfluor normal octane sulfonate, two (4-tert-butyl-phenyl) iodine 2-dicyclos [2.2.1] heptan-2-base-1,1,2,2-HFC-134a sulfonate, two (4-tert-butyl-phenyl) iodine 2-(3-Fourth Ring [4.4.0.1 2,5.1 7,10] dodecyl)-1,1-Difluoroethane sulfonate, two (4-tert-butyl-phenyl) iodine N, N-two (nine fluorine normal butane sulfonyls) imido hydrochlorate, two (4-tert-butyl-phenyl) iodine camsilate,
1-(4-n-butoxy naphthalene-1-yl) thiophane trifluoro-methanyl sulfonate, 1-(4-n-butoxy naphthalene-1-yl) thiophane nine fluorine normal butane sulfonate, 1-(4-n-butoxy naphthalene-1-yl) thiophane perfluor normal octane sulfonate, 1-(4-n-butoxy naphthalene-1-yl) thiophane 2-dicyclo [2.2.1] heptan-2-base-1,1,2,2-HFC-134a sulfonate, 1-(4-n-butoxy naphthalene-1-yl) thiophane 2-(3-Fourth Ring [4.4.0.1 2,5.1 7,10] dodecyl)-1,1-Difluoroethane sulfonate, 1-(4-n-butoxy naphthalene-1-yl) thiophane N, two (nine fluorine normal butane sulfonyls) the imido hydrochlorates of N-, 1-(4-n-butoxy naphthalene-1-yl) thiophane camsilate,
1-(3,5-dimethyl-4-hydroxy phenyl) thiophane trifluoro-methanyl sulfonate, 1-(3,5-dimethyl-4-hydroxy phenyl) thiophane nine fluorine normal butane sulfonate, 1-(3,5-dimethyl-4-hydroxy phenyl) thiophane perfluor normal octane sulfonate, 1-(3,5-dimethyl-4-hydroxy phenyl) thiophane 2-dicyclo [2.2.1] heptan-2-base-1,1,2,2-HFC-134a sulfonate, 1-(3,5-dimethyl-4-hydroxy phenyl) thiophane 2-(3-Fourth Ring [4.4.0.1 2,5.1 7,10] dodecyl)-1,1-Difluoroethane sulfonate, 1-(3,5-dimethyl-4-hydroxy phenyl) thiophane N, two (nine fluorine normal butane sulfonyls) the imido hydrochlorates of N-, 1-(3,5-dimethyl-4-hydroxy phenyl) thiophane camsilate,
N-(fluoroform sulfonyloxy) succinimide, N-(nine fluorine normal butane sulfonyloxies) succinimide, N-(perfluor normal octane sulfonyloxy) succinimide, N-(2-dicyclo [2.2.1] heptan-2-base-1,1,2,2-HFC-134a sulfonyloxy) succinimide, N-(2-(3-Fourth Ring [4.4.0.1 2,5.1 7,10] dodecyl)-1,1-Difluoroethane sulfonyloxy) succinimide, N-(camphor sulfonyloxy) succinimide,
N-(fluoroform sulfonyloxy) dicyclo [2.2.1] heptan-5-alkene-2,3-dicarboxyl acid imide, N-(nine fluorine normal butane sulfonyloxies) dicyclo [2.2.1] heptan-5-alkene-2,3-dicarboxyl acid imide, N-(perfluor normal octane sulfonyloxy) dicyclo [2.2.1] heptan-5-alkene-2,3-dicarboxyl acid imide, N-(2-dicyclo [2.2.1] heptan-2-base-1,1,2,2-HFC-134a sulfonyloxy) dicyclo [2.2.1] heptan-5-alkene-2,3-dicarboxyl acid imide, N-(2-(3-Fourth Ring [4.4.0.1 2,5.1 7,10] dodecyl)-1,1-Difluoroethane sulfonyloxy) dicyclo [2.2.1] heptan-5-alkene-2,3-dicarboxyl acid imide, N-(camphor sulfonyloxy) dicyclo [2.2.1] heptan-5-alkene-2,3-dicarboxyl acid imide etc.
Radiation-sensitive acid among the present invention produces agent can separately or be mixed more than 2 kinds and use.
The use amount that radiation-sensitive acid produces agent is from the susceptibility of guaranteeing resist and the viewpoint of development, and its resin that contains the acid dissociation group with respect to 100 weight portions is generally 0.1～20 weight portion, is preferably 0.1～7 weight portion.In this case, radiation-sensitive acid produces the use amount of agent less than 0.1 weight portion, and susceptibility and development can reduce, and surpasses 20 weight portions on the other hand, and its transparency to radioactive ray reduces, and is difficult to obtain the resist of rectangular patterns.
Preferred acid mixture diffusion control agent in the radiation-sensitive resin composition of the present invention, its have acid producing agent that control causes by exposure produce acid in resist coating diffusion and be suppressed at the not effect of preferred chemical reaction of non-exposure field.
By mixing so sour diffusion control agent, can further improve the storage-stable of the radiation-sensitive resin composition that obtains, can also further improve the resolution of resist, the line width variation that can suppress simultaneously the corrosion-resisting pattern that causes by variation, thereby the very good composition of acquisition processing stability from the indwelling time (PED) till development treatment that exposes.
Be preferably the organic compounds containing nitrogen that does not change by exposure in the corrosion-resisting pattern formation step and heat treated alkalescence as sour diffusion control agent.
Can enumerate " tertiary amine compound ", " compound that contains acylamino-", " quaternary ammonium hydroxide compound ", " nitrogen-containing heterocycle compound " etc. as such a organic compounds containing nitrogen.
For example three (ring) alkyl amines such as triethylamine, Tri-n-Propylamine, tri-n-butylamine, tri-n-amyl amine, three n-hexylamines, three positive heptyl amices, tri-n-octyl amine, tri-n-nonylamine, three n-Decylamines, cyclohexyl dimethylamine, dicyclohexyl methylamine, tricyclohexyltin amine can have been enumerated as " tertiary amine compound "; Aniline, methylphenylamine, N, accelerine, 2-aminotoluene, 3-methylaniline, 4-methylaniline, 4-nitroaniline, 2,6-xylidin, 2, aromatic amines such as 6-diisopropyl aniline, biphenylamine, triphenylamine, naphthylamines; Alkanol such as triethanolamine, diethanolaniline amine; N, N, N ', N '-tetramethylethylenediamine, N, N, N ', N '-four (2-hydroxypropyl) ethylenediamine, 1, two [1-(4-aminophenyl)-1-Methylethyl] the benzene tetra-methylenedimines of 3-, 2, two (4-aminophenyl) propane of 2-, 2-(3-aminophenyl)-2-(4-aminophenyl) propane, 2-(4-aminophenyl)-2-(3-hydroxy phenyl) propane, 2-(4-aminophenyl)-2-(4-hydroxy phenyl) propane, 1, two [1-(4-the aminophenyl)-1-Methylethyl] benzene of 4-, 1, two [1-(4-the aminophenyl)-1-Methylethyl] benzene of 3-, two (2-dimethyl aminoethyl) ether, two (2-diethylamino ethyl) ether etc.
Can enumerate for example N-tert-butoxycarbonyl di-n-octyl amine as " compound that contains acylamino-", N-tert-butoxycarbonyl two n-nonyl amine, N-tert-butoxycarbonyl two positive decyl amine, N-tert-butoxycarbonyl dicyclohexyl amine, N-tert-butoxycarbonyl-1-adamantanamines, N-tert-butoxycarbonyl-N-methyl isophthalic acid-adamantanamines, N, N-two tert-butoxycarbonyls-1-adamantanamines, N, N-two tert-butoxycarbonyls-N-methyl isophthalic acid-adamantanamines, N-tert-butoxycarbonyl-4,4 '-diaminodiphenyl-methane, N, N '-two tert-butoxycarbonyl hexamethylene diamine, N, N, N ', N '-four tert-butoxycarbonyl hexamethylene diamine, N, N '-two tert-butoxycarbonyl-1,7-diamido heptane, N, N '-two tert-butoxycarbonyl-1,8-diamido octane, N, N '-two tert-butoxycarbonyl-1,9-diamido nonane, N, N '-two tert-butoxycarbonyl-1, the 10-diamino decane, N, N '-two tert-butoxycarbonyl-1,12-diamido dodecane, 1-(tert-butoxycarbonyl)-2-pyrrolidine carbinol, the tert-butyl group (tetrahydrochysene-2-oxo-3-furyl) carbamate, N, N '-two tert-butoxycarbonyl-4,4 '-diaminodiphenyl-methane, N-tert-butoxycarbonyl benzimidazole, N-tert-butoxycarbonyl-2-tolimidazole, N-tert-butoxycarbonyl-2-Phenylbenzimidazole etc. contains the amino-compound of N-tert-butoxycarbonyl etc.
For example tetramethyl-ammonium oxyhydroxide, tetraethyl ammonium oxyhydroxide, four n-pro-pyl ammonium oxyhydroxide, tetra-n-butyl ammonium oxyhydroxide etc. can have been enumerated as " quaternary ammonium hydroxide compound ".
As " nitrogenous heterogeneous ring compound " can have been enumerated for example imidazoles such as imidazoles, 4-methylimidazole, 1 benzyl 2 methyl imidazole, 4-methyl-2-phenylimidazole, benzimidazole, 2-Phenylbenzimidazole; Pyridines such as pyridine, 2-picoline, 4-picoline, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, 2-methyl-4-phenylpyridine, nicotine, Nicotinicum Acidum, Nicotinicum Acidum acid amides, quinoline, 4-hydroxyquinoline, 8-Oxoquinoline, acridine; Piperazines such as piperazine, 1-(2-hydroxyethyl) piperazine, also have pyrazine, pyrazoles, pyridazine, キ ノ ザ リ Application, purine, pyrrolidine, piperidines, 3-piperidyl-1 in addition, 2-propylene glycol, morpholine, 4-methyl morpholine, 1,4-lupetazin, 1,4-diazabicyclo [2.2.2] octane etc.
In these organic compounds containing nitrogens, preferred tertiary amine compound, the compound that contains acylamino-, nitrogen-containing heterocycle compound etc., and in containing the compound of acylamino-, preferably contain the amino-compound of N-tert-butoxycarbonyl, preferred imidazoles in the nitrogen-containing heterocycle compound.
The agent of acid diffusion control can separately or mix more than 2 kinds and use.
The combined amount of acid diffusion control agent is generally 15 weight portions or following, preferred 10 weight portions or following, more preferably 5 weight portions or following with respect to the resin of 100 weight portions.In this case, the combined amount of sour diffusion control agent surpasses 15 weight portions, and the susceptibility of resist and the development of exposed portion can reduce.In addition, the combined amount of sour diffusion control agent is less than 0.001 weight portion, has the pattern form of resist and the size worry according to the degree of conformity of processing conditions.
And, in order to demonstrate the effect that more improves anti-cohesive of daring erosion property, pattern form and substrate etc., can in radiation-sensitive resin composition of the present invention, mix and contain/do not contain the adjuvant of acid dissociation organic group.
Can enumerate for example 1-adamantanecarboxylic acid tert-butyl ester as such adjuvant, 1-adamantanecarboxylic acid tert-butoxycarbonyl methyl esters, 1-adamantanecarboxylic acid α-butyrolactone, 1,3-diamantane di-tert-butyl dicarboxylate, the 1-adamantane acetic acid tert-butyl ester, 1-adamantane acetic acid tert-butoxycarbonyl methyl esters, 1,3-diamantane oxalic acid di tert butyl carbonate, 2,5-dimethyl-2,5-two (adamantyl ketonic oxygen base) hexane, the deoxycholic acid tert-butyl ester, deoxycholic acid tert-butoxycarbonyl methyl esters, deoxycholic acid 2-ethoxy ethyl ester, deoxycholic acid 2-cyclohexyl hydroxyl ethyl ester, deoxycholic acid 3-oxo cyclohexyl, the deoxycholic acid tetrahydropyrans ester, deoxycholic acid first hydroxyl levulinic acid ester, the lithocholic acid tert-butyl ester, lithocholic acid tert-butoxycarbonyl methyl esters, lithocholic acid 2-ethoxy ethyl ester, lithocholic acid 2-cyclohexyl hydroxyl ethyl ester, lithocholic acid 3-oxo cyclohexyl, the lithocholic acid tetrahydropyrans ester, lithocholic acid first hydroxyl levulinic acid ester, the hexanedioic acid dimethyl ester, the hexanedioic acid diethylester, the hexanedioic acid dipropyl, the hexanedioic acid di-n-butyl, hexanedioic acid di tert butyl carbonate etc.
These alicyclic adjuvants can separately or mix more than 2 kinds and use.
The combined amount of alicyclic adjuvant is generally below 50 weight portions with respect to 100 parts by weight resin, is preferably below 30 weight portions.In this case, the combined amount of alicyclic adjuvant surpasses 50 weight portions, and the thermotolerance of resist has the tendency of reduction.
In addition, radiation-sensitive resin composition energy mixture table of the present invention reveals the surfactant of effects such as improving coating, development.
Can enumerate for example polyoxyethylene bay ether as surfactant, the polyoxyethylene stearyl ether, polyoxyethylene oil alkene ether, polyoxyethylene n-octyl phenyl ether, polyoxyethylene n-nonyl phenyl ether, polyethylene glycol dilaurate, nonionics such as polyglycol distearate are surfactant, also have following trade name KP341 (manufacturing of chemical industrial company of SHIN-ETSU HANTOTAI) in addition, Port リ Off ロ-No.75 and No.95 (manufacturing of chemical company of common prosperity society), エ Off ト Star プ EF301 and EF303, EF352 (ト-ケ system プ ロ ダ Network Star company makes), メ ガ Off ア Star Network ス F171 and F173 (big Japanese ink chemical industrial company makes), Off ロ ラ-De FC430 and FC431 (Sumitomo ス リ-エ system company makes), ア サ ヒ ガ-De AG710, サ-Off ロ Application S-382 and SC-101, SC-102, SC-103, SC-104, SC-105, SC-106 (manufacturing of Asahi Glass company) etc.
These surfactants can separately or mix more than 2 kinds and use.The combined amount of surfactant with respect to the resin of 100 weight portions usually below 2 weight portions.
In addition, the sensitizer that can mixed display in the radiation-sensitive resin composition of the present invention improves effect such as susceptibility.Preferred sensitizer can have been enumerated for example carbazoles, benzophenone, Rose Bengal class, anthracene class, phenols etc.These sensitizers can separately or mix more than 2 kinds and use.The combined amount of sensitizer is preferably below 50 weight portions with respect to the resin of per 100 weight portions.
And then, halation be can enumerate as the adjuvant beyond above-mentioned and agent, bonding agent, storage-stable agent, defoamer etc. prevented.
Radiation-sensitive resin composition of the present invention is dissolved in use and makes the total solid constituent concentration be generally 3～50 weight % in the solvent, and preferred 5～25 weight % then, are that filtrator about 0.2 μ m filters and prepares composition solution by for example aperture.
Can enumerate for example methyl-n-butyl ketone as the solvent that in the composition solution preparation, uses, the 2-heptanone, methyln-hexyl ketone, cyclopentanone, cyclohexanone, propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate, the 2 hydroxy propanoic acid methyl, the 2 hydroxy propanoic acid ethyl, 3-ethoxy-c acid methyl, 3-ethoxy-propionic acid ethyl, glycol monoethyl ether, ethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, dihydroxypropane single-ether, ro-butyl acetate, the pyruvic acid methyl ester, the pyruvic acid ethyl ester, N-Methyl pyrrolidone, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, gamma-butyrolacton etc.
These solvents can separately or mix more than 2 kinds and use, preferred 2-heptanone, cyclohexanone, propylene glycol methyl ether acetate, 2 hydroxy propanoic acid ethyl ester, 3-ethoxy-propionic acid ethyl ester, propylene glycol monomethyl ether, gamma-butyrolacton in these examples.
Radiation-sensitive resin composition of the present invention is particularly suitable for chemically amplified corrosion-resisitng agent.For chemically amplified corrosion-resisitng agent, it is by exposure, effect by the acid that acid producing agent is produced, acid dissociation group in the resin is dissociated, produce carboxyl, the part of resist exposure as a result uprises the dissolubility of alkaline-based developer, by this exposed portion of dissolving in alkaline-based developer, and the corrosion-resisting pattern of the eurymeric that can be removed.
When forming corrosion-resisting pattern by radiation-sensitive resin composition of the present invention, by suitable coating means such as rotary coating, curtain coating coating, roller coating, sprayings, coating composition solution on for example passing through at silicon chip, with the substrates such as wafer of aluminium coating, form against corrosion filming, according to circumstances preheat and handle back (hereinafter referred to as " PB "), then, make this exposure of filming against corrosion, to form the regulation corrosion-resisting pattern.At this moment the radioactive ray of the Shi Yonging selection that can suit is ultraviolet ray, KrF excimer laser (wavelength 248nm), ArF excimer laser (wavelength 193nm), F for example 2Excimer laser (wavelength 157nm), EUV X ray such as charged particle rays such as far ultraviolet, electron ray, synchrotron radioactive ray such as (extreme ultraviolet light, wavelength 13nm etc.) wait and use, but this wherein preferred far ultraviolet, electron ray.And conditions of exposures such as exposure wait suitable the selection according to the mixing composition of radiation-sensitive resin composition, the kind of each adjuvant.
In order stably to form high-precision fine pattern, preferably after exposure, carry out heat treated (hereinafter referred to as " PEB ") among the present invention.By this PEB, the dissociation reaction of the acid dissociation organic group in the resin can carry out reposefully.The heating condition of PEB is adjusted according to the mixing composition of radiation-sensitive resin composition, is generally 30～200 ℃, preferred 50～170 ℃.
Among the present invention; in order to bring into play the potentiality of radiation-sensitive resin composition to greatest extent; also can as the spy open in flat 6-12452 communique etc. disclosed; on employed substrate, be pre-formed the antireflection film of organic system or inorganic system; in addition for the influence of alkaline impurities of preventing to contain in the environment gas etc.; also can as the spy open in flat 5-188598 communique etc. disclosed, on against corrosion filming, be provided with diaphragm, perhaps these two kinds of technology are used in combination.
Then, by making the film development that is coated with against corrosion after the exposure, form the corrosion-resisting pattern of regulation.
As the developer solution that uses in development, preference is as having dissolved the alkaline aqueous solution of Tetramethylammonium hydroxide.The concentration of alkaline aqueous solution is usually below 10 weight %.In this case, the concentration of alkaline aqueous solution surpasses 10 weight %, has the worry that non-exposed portion also is dissolved in developer solution, is not preferred.In addition, also can add an amount of surfactant etc. in the developer solution that makes by alkaline aqueous solution.In addition, behind the developing liquid developing that makes with alkaline aqueous solution, general water cleans and is dry.
Embodiment
Below enumerate embodiment and specify the present invention.Here, do not specify that part is a weight portion.
In embodiment and the comparative example each measured, estimated and undertaken by following method.
(1) Mw, Mn and to the conversion ratio of polymkeric substance:
Use the GPC post that eastern Cao company makes (G2000HXL2 props up, 1 of G3000HXL, 1 of G4000HXL), at flow is that 1.0 ml/min, eluting solvent are tetrahydrofuran, under the analysis condition that column temperature is 40 ℃, as the standard reference material, (GPC) measures by gel permeation chromatography with monodisperse polystyrene.Conversion ratio to polymkeric substance is calculated according to the area ratio at each peak.
(2) susceptibility
Under the situation of exposing with the ArF light source, use the thickness that on wafer surface, forms silicon chip (ARC29) as ARC29 (manufacturing of the Brewer Science company) film of 78nm, by spin-coating method each composition solution is coated on the substrate, carrying out the against corrosion of thickness 340nm that PB forms with the condition shown in the table 4 on electric hot plate films, ArF excimer laser exposure device (lens opening numerical value is 0.55) with Nikon company makes exposes by mask pattern.Then, carry out PEB under the conditions shown in Table 4 after, developed 60 seconds down at 25 ℃ with the tetramethylammonium hydroxide aqueous solution of 2.38 weight %, water cleans and is dry, forms the corrosion-resisting pattern of eurymeric.At this moment, (1L1S) exposure of pattern is as optimum exposure will to form the line-blank (Space) with live width 160nm with 1 pair 1 live width, and this optimum exposure is as susceptibility.
(3) observation of sidewall roughness (LER):
In the observation of the 160nm1L/1S pattern of under optimum exposure, differentiating, when the long SEM:S9220 of survey of use Hitachi, Ltd system observes from pattern top,, represent that with 3 ∑s this mensuration is uneven from any point observation live width.
(4) poor between the molecular weight group
Each synthesis example is synthesized the resins that contain the acid dissociation group 5 times under the same conditions, measure the Mw of the resin that obtains respectively.Obtain and measure several 5 standard deviation, it is poor to obtain between the molecular weight group.
Synthesis example 1
Figure G2003801077532D00371
In 200g toluene, dissolve the compound (S1-1) of 42.87g (40 moles of %), the compound (S2-1) of 57.13g (60 moles of %), the 2 bromopropionic acid 2-hydroxyl ethyl ester of 100g toluene and 2.71g, two (triphenylphosphine) rutheniums of 10.63g chlorine indenyl, 2.38g pentamethyl Diethylenetriamine joined in 1000 milliliters the three-neck flask, with nitrogen purge 30 minutes.After the nitrogen purge, reactor is heated to 110 ℃ while stirring, uses tap funnel with 3 hours above-mentioned monomer solutions of dropping preprepared.To drip the time that beginning begins as polymerization, implemented polyreaction 48 hours.Polymerization is cooled to polymeric solution below 30 ℃ by water cooling after stopping, and puts in the 2000g methyl alcohol, filters the white powder of separating out., after cleaning the white powder that is filtered on the slurries, filter with the methyl alcohol of 400g 2 times, 50 ℃ dry 17 hours down, obtain the resin (78g, productive rate 78%) of white powder.The Mw=6600 of this resin, Mw/Mn=1.37, each the repetitive containing ratio of repetitive that is compound (S1-1), compound (S2-1) expression are the multipolymer of 39.1: 60.9 (mole %).This resin is as resin (A-1).
Synthesis example 2
In 200g toluene, dissolve the compound (S1-2) of 42.87g (40 moles of %), the compound (S2-2) of 57.13g (60 moles of %); the 2-methoxyl of 100g toluene and 2.86g sulfuration carbonyl sulfanilyl radical-ethyl propionate joined in 1000 milliliters the three-neck flask, with nitrogen purge 30 minutes.After the nitrogen purge, reactor is heated to 110 ℃ while stirring, uses tap funnel with 3 hours above-mentioned monomer solutions of dropping preprepared.To drip the time that beginning begins as polymerization, implemented polyreaction 48 hours.Polymerization is cooled to polymeric solution below 30 ℃ by water cooling after stopping, and puts in the 2000g methyl alcohol, filters the white powder of separating out., behind the white powder of cleaning and filtering on the slurries, filter with the methyl alcohol of 400g 2 times, 50 ℃ dry 17 hours down, obtain the resin (75g, productive rate 75%) of white powder.The Mw=7000 of this resin, Mw/Mn=1.28, repetitive, each the repetitive containing ratio that is compound (S1-2), compound (S2-2) expression are the multipolymer of 39.1: 60.9 (mole %).This resin is as resin (A-2).
Synthesis example
Figure G2003801077532D00382
In 200g toluene, dissolve the compound (S1-3) of 42.87g (40 moles of %), the compound (S2-3) of 57.13g (60 moles of %), 2-(2 with 100g toluene and 3.34g, 2,6,6-tetramethyl-piperidines-1-base hydroxyl)-methyl propionate joined in 1000 milliliters the three-neck flask, with nitrogen purge 30 minutes.After the nitrogen purge, reactor is heated to 110 ℃ while stirring, uses tap funnel with 3 hours above-mentioned monomer solutions of dropping preprepared.To drip the time that beginning begins as polymerization, implemented polyreaction 48 hours.Polymerization is cooled to polymeric solution below 30 ℃ by water cooling after stopping, and puts in the 2000g methyl alcohol, filters the white powder of separating out., behind the white powder of cleaning and filtering on the slurries, filter with the methyl alcohol of 400g 2 times, 50 ℃ dry 17 hours down, obtain the resin (80g, productive rate 80%) of white powder.The Mw=7800 of this resin, Mw/Mn=1.45, repetitive, each the repetitive containing ratio that is compound (S1-3), compound (S2-3) expression are the multipolymer of 39.1: 60.9 (mole %).This resin is resin (A-3).
Synthesis example 4
Figure G2003801077532D00391
In 200g toluene, dissolve the compound (S1-4) of 42.69g (40 moles of %), the compound (S2-4) of 57.31g (60 moles of %), the 2 bromopropionic acid 2-hydroxyl ethyl ester of 100g toluene and 2.55g, two (triphenylphosphine) rutheniums of 9.99g chlorine indenyl, 2.24g pentamethyl Diethylenetriamine joined in 1000 milliliters the three-neck flask, with nitrogen purge 30 minutes.After the nitrogen purge, reactor is heated to 110 ℃ while stirring, uses tap funnel with 3 hours above-mentioned monomer solutions of dropping preprepared.To drip the time that beginning begins as polymerization, implemented polyreaction 48 hours.Polymerization is cooled to polymeric solution below 30 ℃ by water cooling after stopping, and puts in the 2000g methyl alcohol, filters the white powder of separating out., behind the white powder of cleaning and filtering on the slurries, filter with the methyl alcohol of 400g 2 times, 50 ℃ dry 17 hours down, obtain the resin (78g, productive rate 78%) of white powder.The Mw=7400 of this resin, Mw/Mn=1.40, repetitive, each the repetitive containing ratio that is compound (S1-4), compound (S2-4) expression are the multipolymer of 38.5: 61.5 (mole %).This resin is resin (A-4).
Synthesis example 5
In 200g toluene, dissolve the compound (S1-5) of 40.01g (40 moles of %), the compound (S2-5) of 59.99g (60 moles of %), the 2 bromopropionic acid 2-hydroxyl ethyl ester of 100g toluene and 2.67g, two (triphenylphosphine) rutheniums of 10.46g chlorine indenyl, 2.34g pentamethyl Diethylenetriamine joined in 1000 milliliters the three-neck flask, with nitrogen purge 30 minutes.After the nitrogen purge, reactor is heated to 110 ℃ while stirring, uses tap funnel with 3 hours above-mentioned monomer solutions of dropping preprepared.To drip the time that beginning begins as polymerization, implemented polyreaction 48 hours.Polymerization is cooled to polymeric solution below 30 ℃ by water cooling after stopping, and puts in the 2000g methyl alcohol, filters the white powder of separating out., behind the white powder of cleaning and filtering on the slurries, filter with the methyl alcohol of 400g 2 times, 50 ℃ dry 17 hours down, obtain the resin (76g, productive rate 76%) of white powder.The Mw=7600 of this resin, Mw/Mn=1.41, repetitive, each the repetitive containing ratio that is compound (S1-5), compound (S2-5) expression are the multipolymer of 39.1: 60.9 (mole %).This resin is resin (A-5).
Synthesis example 6
In 200g toluene, dissolve the compound (S1-6) of 44.30g (40 moles of %), the compound (S2-6) of 55.70g (60 moles of %), the 2 bromopropionic acid 2-hydroxyl ethyl ester of 100g toluene and 2.64g, two (triphenylphosphine) rutheniums of 10.37g chlorine indenyl, 2.32g pentamethyl Diethylenetriamine joined in 1000 milliliters the three-neck flask, with nitrogen purge 30 minutes.After the nitrogen purge, reactor is heated to 110 ℃ while stirring, uses tap funnel with 3 hours above-mentioned monomer solutions of dropping preprepared.To drip the time that beginning begins as polymerization, implemented polyreaction 48 hours.Polymerization is cooled to polymeric solution below 30 ℃ by water cooling after stopping, and puts in the 2000g methyl alcohol, filters the white powder of separating out., behind the white powder of cleaning and filtering on the slurries, filter with the methyl alcohol of 400g 2 times, 50 ℃ dry 17 hours down, obtain the resin (76g, productive rate 76%) of white powder.The Mw=6500 of this resin, Mw/Mn=1.35, repetitive, each the repetitive containing ratio that is compound (S1-6), compound (S2-6) expression are the multipolymer of 38.5: 61.5 (mole %).This resin is resin (A-6).
Synthesis example 7
Figure G2003801077532D00412
In 200g toluene, dissolve the compound (S1-7) of 41.28g (40 moles of %), the compound (S2-7) of 58.72g (60 moles of %), the 2 bromopropionic acid 2-hydroxyl ethyl ester of 100g toluene and 2.71g, two (triphenylphosphine) rutheniums of 10.63g chlorine indenyl, 2.38g pentamethyl Diethylenetriamine joined in 1000 milliliters the three-neck flask, with nitrogen purge 30 minutes.After the nitrogen purge, reactor is heated to 110 ℃ while stirring, uses tap funnel with 3 hours above-mentioned monomer solutions of dropping preprepared.To drip the time that beginning begins as polymerization, implemented polyreaction 48 hours.Polymerization is cooled to polymeric solution below 30 ℃ by water cooling after stopping, and puts in the 2000g methyl alcohol, filters the white powder of separating out., behind the white powder of cleaning and filtering on the slurries, filter with the methyl alcohol of 400g 2 times, 50 ℃ dry 17 hours down, obtain the resin (77g, productive rate 77%) of white powder.The Mw=7700 of this resin, Mw/Mn=1.46 is that the repetition of compound (S1-7), compound (S2-7) expression is single, each repetitive containing ratio of unit is the multipolymer of 38.5: 61.5 (mole %).This resin is resin (A-7).
Synthesis example 8
Figure G2003801077532D00421
In 200g toluene, dissolve the compound (S1-8) of 35.88g (35 moles of %), the compound (S2-8) of 48.61g (50 moles of %), the compound (S3-8) of 15.51g (15 moles of %), the 2 bromopropionic acid 2-hydroxyl ethyl ester of 100g toluene and 2.16g, two (triphenylphosphine) rutheniums of 8.48g chlorine indenyl, 1.90g pentamethyl Diethylenetriamine joined in 1000 milliliters the three-neck flask, with nitrogen purge 30 minutes.After the nitrogen purge, reactor is heated to 110 ℃ while stirring, uses tap funnel with 3 hours above-mentioned monomer solutions of dropping preprepared.To drip the time that beginning begins as polymerization, implemented polyreaction 48 hours.Polymerization is cooled to polymeric solution below 30 ℃ by water cooling after stopping, and puts in the 2000g methyl alcohol, filters the white powder of separating out., behind the white powder of cleaning and filtering on the slurries, filter with the methyl alcohol of 400g 2 times, 50 ℃ dry 17 hours down, obtain the resin (72g, productive rate 72%) of white powder.The Mw=7800 of this resin, Mw/Mn=1.44, repetitive, each the repetitive containing ratio that is compound (S1-8), compound (S 2-8), compound (S3-8) expression are the multipolymer of 34.0: 51.1: 14.9 (mole %).This resin is resin (A-8).
Synthesis example 9
Figure G2003801077532D00431
In 200g toluene, dissolve the compound (S1-9) of 38.52g (35 moles of %), the compound (S2-9) of 46.61g (50 moles of %), the compound (S3-9) of 14.87g (15 moles of %), the 2 bromopropionic acid 2-hydroxyl ethyl ester of 100g toluene and 2.07g, two (triphenylphosphine) rutheniums of 8.13g chlorine indenyl, 1.82g pentamethyl Diethylenetriamine joined in 1000 milliliters the three-neck flask, with nitrogen purge 30 minutes.After the nitrogen purge, reactor is heated to 110 ℃ while stirring, uses tap funnel with 3 hours above-mentioned monomer solutions of dropping preprepared.To drip the time that beginning begins as polymerization, implemented polyreaction 48 hours.Polymerization is cooled to polymeric solution below 30 ℃ by water cooling after stopping, and puts in the 2000g methyl alcohol, filters the white powder of separating out., behind the white powder of cleaning and filtering on the slurries, filter with the methyl alcohol of 400g 2 times, 50 ℃ dry 17 hours down, obtain the resin (73g, productive rate 73%) of white powder.The Mw=8000 of this resin, Mw/Mn=1.46, repetitive, each the repetitive containing ratio that is compound (S1-9), compound (S2-9), compound (S3-9) expression are the multipolymer of 34.2: 51.0: 14.8 (mole %).This resin is resin (A-9).
Synthesis example 10
In 200g toluene, dissolve the compound (S1-10) of 37.23g (35 moles of %), the compound (S2-10) of 47.59g (50 moles of %), the compound (S3-10) of 15.18g (15 moles of %), the 2 bromopropionic acid 2-hydroxyl ethyl ester of 100g toluene and 2.12g, two (triphenylphosphine) rutheniums of 8.30g chlorine indenyl, 1.86g pentamethyl Diethylenetriamine joined in 1000 milliliters the three-neck flask, with nitrogen purge 30 minutes.After the nitrogen purge, reactor is heated to 110 ℃ while stirring, uses tap funnel with 3 hours above-mentioned monomer solutions of dropping preprepared.To drip the time that beginning begins as polymerization, implemented polyreaction 48 hours.Polymerization is cooled to polymeric solution below 30 ℃ by water cooling after stopping, and puts in the 2000g methyl alcohol, filters the white powder of separating out., behind the white powder of cleaning and filtering on the slurries, filter with the methyl alcohol of 400g 2 times, 50 ℃ dry 17 hours down, obtain the resin (73g, productive rate 73%) of white powder.The Mw=7800 of this resin, Mw/Mn=1.48, repetitive, each the repetitive containing ratio that is compound (S1-10), compound (S2-10), compound (S3-10) expression are the multipolymer of 33.2: 51.5: 15.3 (mole %).This resin is resin (A-10).
Synthesis example 11
In 200g toluene, dissolve the compound (S1-11) of 35.88g (35 moles of %), the compound (S2-11) of 48.61g (50 moles of %), the compound (S3-11) of 15.51g (15 moles of %), the 2 bromopropionic acid 2-hydroxyl ethyl ester of 100g toluene and 2.16g, two (triphenylphosphine) rutheniums of 8.48g chlorine indenyl, 1.90g pentamethyl Diethylenetriamine joined in 1000 milliliters the three-neck flask, with nitrogen purge 30 minutes.After the nitrogen purge, reactor is heated to 110 ℃ while stirring, uses tap funnel with 3 hours above-mentioned monomer solutions of dropping preprepared.To drip the time that beginning begins as polymerization, implemented polyreaction 48 hours.Polymerization is cooled to polymeric solution below 30 ℃ by water cooling after stopping, and puts in the 2000g methyl alcohol, filters the white powder of separating out., behind the white powder of cleaning and filtering on the slurries, filter with the methyl alcohol of 400g 2 times, 50 ℃ dry 17 hours down, obtain the resin (73g, productive rate 73%) of white powder.The Mw=8500 of this resin, Mw/Mn=1.42, repetitive, each the repetitive containing ratio that is compound (S1-11), compound (S2-11), compound (S3-11) expression are the multipolymer of 34.0: 51.0: 15.0 (mole %).This resin is resin (A-11).
Synthesis example 12
Figure G2003801077532D00451
In 200g toluene, dissolve the compound (S1-12) of 37.32g (35 moles of %), the compound (S2-12) of 47.37g (50 moles of %), the compound (S3-12) of 15.31g (15 moles of %), the 2 bromopropionic acid 2-hydroxyl ethyl ester of 100g toluene and 2.61g, two (triphenylphosphine) rutheniums of 10.24g chlorine indenyl, 2.29g pentamethyl Diethylenetriamine joined in 1000 milliliters the three-neck flask, with nitrogen purge 30 minutes.After the nitrogen purge, reactor is heated to 110 ℃ while stirring, uses tap funnel with 3 hours above-mentioned monomer solutions of dropping preprepared.To drip the time that beginning begins as polymerization, implemented polyreaction 48 hours.Polymerization is cooled to polymeric solution below 30 ℃ by water cooling after stopping, and puts in the 2000g methyl alcohol, filters the white powder of separating out., behind the white powder of cleaning and filtering on the slurries, filter with the methyl alcohol of 400g 2 times, 50 ℃ dry 17 hours down, obtain the resin (72g, productive rate 72%) of white powder.The Mw=8100 of this resin, Mw/Mn=1.33, repetitive, each the repetitive containing ratio that is compound (S1-12), compound (S2-12), compound (S3-12) expression are the multipolymer of 34.5: 50.5: 15.0 (mole %).This resin is resin (A-12).
Synthesis example 13
Figure G2003801077532D00461
In 200g toluene, dissolve the compound (S1-13) of 34.68g (35 moles of %), the compound (S2-13) of 49.52g (50 moles of %), the compound (S3-13) of 15.80g (15 moles of %), the 2 bromopropionic acid 2-hydroxyl ethyl ester of 100g toluene and 2.20g, two (triphenylphosphine) rutheniums of 8.63g chlorine indenyl, 1.93g pentamethyl Diethylenetriamine joined in 1000 milliliters the three-neck flask, with nitrogen purge 30 minutes.After the nitrogen purge, reactor is heated to 110 ℃ while stirring, uses tap funnel with 3 hours above-mentioned monomer solutions of dropping preprepared.To drip the time that beginning begins as polymerization, implemented polyreaction 48 hours.Polymerization is cooled to polymeric solution below 30 ℃ by water cooling after stopping, and puts in the 2000g methyl alcohol, filters the white powder of separating out., behind the white powder of cleaning and filtering on the slurries, filter with the methyl alcohol of 400g 2 times, 50 ℃ dry 17 hours down, obtain the resin (71g, productive rate 71%) of white powder.The Mw=7900 of this resin, Mw/Mn=1.45 is that repetitive, each repetitive containing ratio of compound (S1-13), compound (S 2-13), compound (S3-13) expression is 34.3: 50.The multipolymer of 6: 15.1 (mole %).This resin is resin (A-13).
Synthesis example 14
Figure G2003801077532D00471
In 200g toluene, dissolve the compound (S1-14) of 28.66g (35 moles of %), the compound (S2-14) of 54.09g (50 moles of %), the compound (S3-14) of 17.25g (15 moles of %), the 2 bromopropionic acid 2-hydroxyl ethyl ester of 100g toluene and 2.41g, two (triphenylphosphine) rutheniums of 9.43g chlorine indenyl, 2.11g pentamethyl Diethylenetriamine joined in 1000 milliliters the three-neck flask, with nitrogen purge 30 minutes.After the nitrogen purge, reactor is heated to 110 ℃ while stirring, uses tap funnel with 3 hours above-mentioned monomer solutions of dropping preprepared.To drip the time that beginning begins as polymerization, implemented polyreaction 48 hours.Polymerization is cooled to polymeric solution below 30 ℃ by water cooling after stopping, and puts in the 2000g methyl alcohol, filters the white powder of separating out., behind the white powder of cleaning and filtering on the slurries, filter with the methyl alcohol of 400g 2 times, 50 ℃ dry 17 hours down, obtain the resin (73g, productive rate 73%) of white powder.The Mw=8500 of this resin, Mw/Mn=1.41, repetitive, each the repetitive containing ratio that is compound (S1-14), compound (S2-14), compound (S3-14) expression are the multipolymer of 34.2: 50.9: 14.9 (mole %).This resin is resin (A-14).
Synthesis example 15
In 200g toluene, dissolve the compound (S1-15) of 30.33g (35 moles of %), the compound (S2-15) of 52.82g (50 moles of %), the compound (S3-15) of 16.85g (15 moles of %), the 2 bromopropionic acid 2-hydroxyl ethyl ester of 100g toluene and 2.35g, two (triphenylphosphine) rutheniums of 9.21g chlorine indenyl, 2.06g pentamethyl Diethylenetriamine joined in 1000 milliliters the three-neck flask, with nitrogen purge 30 minutes.After the nitrogen purge, reactor is heated to 110 ℃ while stirring, uses tap funnel with 3 hours above-mentioned monomer solutions of dropping preprepared.To drip the time that beginning begins as polymerization, implemented polyreaction 48 hours.Polymerization is cooled to polymeric solution below 30 ℃ by water cooling after stopping, and puts in the 2000g methyl alcohol, filters the white powder of separating out., behind the white powder of cleaning and filtering on the slurries, filter with the methyl alcohol of 400g 2 times, 50 ℃ dry 17 hours down, obtain the resin (72g, productive rate 72%) of white powder.The Mw=8100 of this resin, Mw/Mn=1.41, repetitive, each the repetitive containing ratio that is compound (S1-15), compound (S2-15), compound (S3-15) expression are the multipolymer of 34.1: 51.1: 14.8 (mole %).This resin is resin (A-15).
Synthesis example 16
In 200g toluene, dissolve the compound (S1-16) of 35.93g (35 moles of %), the compound (S2-16) of 48.68g (50 moles of %), the compound (S 3-16) of 15.39g (15 moles of %), the 2 bromopropionic acid 2-hydroxyl ethyl ester of 100g toluene and 2.17g, two (triphenylphosphine) rutheniums of 8.49g chlorine indenyl, 1.90g pentamethyl Diethylenetriamine joined in 1000 milliliters the three-neck flask, with nitrogen purge 30 minutes.After the nitrogen purge, reactor is heated to 110 ℃ while stirring, uses tap funnel with 3 hours above-mentioned monomer solutions of dropping preprepared.To drip the time that beginning begins as polymerization, implemented polyreaction 48 hours.Polymerization is cooled to polymeric solution below 30 ℃ by water cooling after stopping, and puts in the 2000g methyl alcohol, filters the white powder of separating out., behind the white powder of cleaning and filtering on the slurries, filter with the methyl alcohol of 400g 2 times, 50 ℃ dry 17 hours down, obtain the resin (74g, productive rate 74%) of white powder.The Mw=8500 of this resin, Mw/Mn=1.49, repetitive, each the repetitive containing ratio that is compound (S1-16), compound (S2-16), compound (S3-16) expression are the multipolymer of 34.0: 50.9: 15.1 (mole %).This resin is resin (A-16).
Synthesis example 17
In 200g toluene, dissolve the compound (S1-17) of 33.18g (35 moles of %), the compound (S2-17) of 44.96g (50 moles of %), the compound (S3-17) of 21.86g (15 moles of %), the 2 bromopropionic acid 2-hydroxyl ethyl ester of 100g toluene and 2.00g, two (triphenylphosphine) rutheniums of 7.84g chlorine indenyl, 1.76g pentamethyl Diethylenetriamine joined in 1000 milliliters the three-neck flask, with nitrogen purge 30 minutes.After the nitrogen purge, reactor is heated to 110 ℃ while stirring, uses tap funnel with 3 hours above-mentioned monomer solutions of dropping preprepared.To drip the time that beginning begins as polymerization, implemented polyreaction 48 hours.Polymerization is cooled to polymeric solution below 30 ℃ by water cooling after stopping, and puts in the 2000g methyl alcohol, filters the white powder of separating out., behind the white powder of cleaning and filtering on the slurries, filter with the methyl alcohol of 400g 2 times, 50 ℃ dry 17 hours down, obtain the resin (73g, productive rate 73%) of white powder.The Mw=8000 of this resin, Mw/Mn=1.46, repetitive, each the repetitive containing ratio that is compound (S1-17), compound (S2-17), compound (S3-17) expression are the multipolymer of 33.8: 51.1: 15.1 (mole %).This resin is resin (A-17).
Synthesis example 18
In 200g toluene, dissolve the compound (S1-18) of 36.50g (35 moles of %), the compound (S2-18) of 49.46g (50 moles of %), the compound (S3-18) of 14.04g (15 moles of %), the 2 bromopropionic acid 2-hydroxyl ethyl ester of 100g toluene and 2.20g, two (triphenylphosphine) rutheniums of 8.62g chlorine indenyl, 1.93g pentamethyl Diethylenetriamine joined in 1000 milliliters the three-neck flask, with nitrogen purge 30 minutes.After the nitrogen purge, reactor is heated to 110 ℃ while stirring, uses tap funnel with 3 hours above-mentioned monomer solutions of dropping preprepared.To drip the time that beginning begins as polymerization, implemented polyreaction 48 hours.Polymerization is cooled to polymeric solution below 30 ℃ by water cooling after stopping, and puts in the 2000g methyl alcohol, filters the white powder of separating out., behind the white powder of cleaning and filtering on the slurries, filter with the methyl alcohol of 400g 2 times, 50 ℃ dry 17 hours down, obtain the resin (74g, productive rate 74%) of white powder.The Mw=7700 of this resin, Mw/Mn=1.45, repetitive, each the repetitive containing ratio that is compound (S1-18), compound (S2-18), compound (S3-18) expression are the multipolymer of 33.9: 51.0: 15.1 (mole %).This resin is resin (A-18).
Synthesis example 19
In 200g toluene, dissolve the compound (S1-19) of 32.73g (35 moles of %), the compound (S2-19) of 53.13g (50 moles of %), the compound (S3-19) of 14.14g (15 moles of %), the 2 bromopropionic acid 2-hydroxyl ethyl ester of 100g toluene and 1.97g, two (triphenylphosphine) rutheniums of 7.73g chlorine indenyl, 1.73g pentamethyl Diethylenetriamine joined in 1000 milliliters the three-neck flask, with nitrogen purge 30 minutes.After the nitrogen purge, reactor is heated to 110 ℃ while stirring, uses tap funnel with 3 hours above-mentioned monomer solutions of dropping preprepared.To drip the time that beginning begins as polymerization, implemented polyreaction 48 hours.Polymerization is cooled to polymeric solution below 30 ℃ by water cooling after stopping, and puts in the 2000g methyl alcohol, filters the white powder of separating out., behind the white powder of cleaning and filtering on the slurries, filter with the methyl alcohol of 400g 2 times, 50 ℃ dry 17 hours down, obtain the resin (70g, productive rate 70%) of white powder.The Mw=8200 of this resin, Mw/Mn=1.46, repetitive, each the repetitive containing ratio that is compound (S1-19), compound (S2-19), compound (S3-19) expression are the multipolymer of 34.4: 50.6: 15.0 (mole %).This resin is resin (A-19).
Synthesis example 20
Figure G2003801077532D00521
In 200g toluene, dissolve the compound (S1-20) of 30.99g (35 moles of %), the compound (S2-20) of 55.61g (50 moles of %), the compound (S3-20) of 13.40g (15 moles of %), the 2 bromopropionic acid 2-hydroxyl ethyl ester of 100g toluene and 1.87g, two (triphenylphosphine) rutheniums of 7.32g chlorine indenyl, 1.64g pentamethyl Diethylenetriamine joined in 1000 milliliters the three-neck flask, with nitrogen purge 30 minutes.After the nitrogen purge, reactor is heated to 110 ℃ while stirring, uses tap funnel with 3 hours above-mentioned monomer solutions of dropping preprepared.To drip the time that beginning begins as polymerization, implemented polyreaction 48 hours.Polymerization is cooled to polymeric solution below 30 ℃ by water cooling after stopping, and puts in the 2000g methyl alcohol, filters the white powder of separating out., behind the white powder of cleaning and filtering on the slurries, filter with the methyl alcohol of 400g 2 times, 50 ℃ dry 17 hours down, obtain the resin (70g, productive rate 70%) of white powder.The Mw=8300 of this resin, Mw/Mn=1.47, repetitive, each the repetitive containing ratio that is compound (S1-20), compound (S2-20), compound (S3-20) expression are the multipolymer of 34.5: 50.5: 15.0 (mole %).This resin is resin (A-20).
Synthesis example 21
Figure G2003801077532D00531
In 200g toluene, dissolve the compound (S2-21) of the compound (S1-21) of 35.60g (35 moles of %), the compound of 16.17g (15 moles of %) (S1-21 '), 48.23g (50 moles of %), the 2 bromopropionic acid 2-hydroxyl ethyl ester of 100g toluene and 2.15g, two (triphenylphosphine) rutheniums of 8.41g chlorine indenyl, 1.88g pentamethyl Diethylenetriamine joined in 1000 milliliters the three-neck flask, with nitrogen purge 30 minutes.After the nitrogen purge, reactor is heated to 110 ℃ while stirring, uses tap funnel with 3 hours above-mentioned monomer solutions of dropping preprepared.To drip the time that beginning begins as polymerization, implemented polyreaction 48 hours.Polymerization is cooled to polymeric solution below 30 ℃ by water cooling after stopping, and puts in the 2000g methyl alcohol, filters the white powder of separating out., behind the white powder of cleaning and filtering on the slurries, filter with the methyl alcohol of 400g 2 times, 50 ℃ dry 17 hours down, obtain the resin (72g, productive rate 72%) of white powder.The Mw=8300 of this resin, Mw/Mn=1.46 is that repetitive, each repetitive containing ratio of compound (S1-21), compound (S1-21 '), compound (S2-21) expression is the multipolymer of 35.0: 14.3: 50.7 (mole %).This resin is resin (A-21).
Synthesis example 22
In 200g toluene, dissolve the compound (S2-22) of the compound (S1-22) of 37.07g (35 moles of %), the compound of 15.89g (15 moles of %) (S1-22 '), 47.05g (50 moles of %), the 2 bromopropionic acid 2-hydroxyl ethyl ester of 100g toluene and 2.23g, two (triphenylphosphine) rutheniums of 8.76g chlorine indenyl, 1.96g pentamethyl Diethylenetriamine joined in 1000 milliliters the three-neck flask, with nitrogen purge 30 minutes.After the nitrogen purge, reactor is heated to 110 ℃ while stirring, uses tap funnel with 3 hours above-mentioned monomer solutions of dropping preprepared.To drip the time that beginning begins as polymerization, implemented polyreaction 48 hours.Polymerization is cooled to polymeric solution below 30 ℃ by water cooling after stopping, and puts in the 2000g methyl alcohol, filters the white powder of separating out., behind the white powder of cleaning and filtering on the slurries, filter with the methyl alcohol of 400g 2 times, 50 ℃ dry 17 hours down, obtain the resin (71g, productive rate 71%) of white powder.The Mw=8300 of this resin, Mw/Mn=1.49 is that repetitive, each repetitive containing ratio of compound (S1-22), compound (S1-22 '), compound (S2-22) expression is the multipolymer of 34.8: 14.8: 50.4 (mole %).This resin is resin (A-22).
Synthesis example 23
In 200g toluene, dissolve the compound (S1-23) of 37.32g (35 moles of %), the compound (S2-23) of 47.37g (50 moles of %), the compound (S3-23) of 15.31g (15 moles of %); 2-dimethyl thiocarbamoyl sulfo group (ス Le Off ア ニ Le)-ethyl propionate of 100g toluene and 2.50g joined in 1000 milliliters the three-neck flask, with nitrogen purge 30 minutes.After the nitrogen purge, reactor is heated to 110 ℃ while stirring, uses tap funnel with 3 hours above-mentioned monomer solutions of dropping preprepared.To drip the time that beginning begins as polymerization, implemented polyreaction 48 hours.Polymerization is cooled to polymeric solution below 30 ℃ by water cooling after stopping, and puts in the 2000g methyl alcohol, filters the white powder of separating out., behind the white powder of cleaning and filtering on the slurries, filter with the methyl alcohol of 400g 2 times, 50 ℃ dry 17 hours down, obtain the resin (75g, productive rate 75%) of white powder.The Mw=7700 of this resin, Mw/Mn=1.26, repetitive, each the repetitive containing ratio that is compound (S1-23), compound (S2-23), compound (S3-23) expression are the multipolymer of 34.5: 50.4: 15.1 (mole %).This resin is resin (A-23).
Synthesis example 24
In 200g toluene, dissolve the compound (S1-24) of 36.46g (35 moles of %), the compound (S2-24) of 49.39g (50 moles of %), the compound (S3-24) of 14.15g (15 moles of %), the 2 bromopropionic acid 2-hydroxyl ethyl ester of 100g toluene and 2.20g, two (triphenylphosphine) rutheniums of 8.61g chlorine indenyl, 1.93g pentamethyl Diethylenetriamine joined in 1000 milliliters the three-neck flask, with nitrogen purge 30 minutes.After the nitrogen purge, reactor is heated to 110 ℃ while stirring, uses tap funnel with 3 hours above-mentioned monomer solutions of dropping preprepared.To drip the time that beginning begins as polymerization, implemented polyreaction 48 hours.Polymerization is cooled to polymeric solution below 30 ℃ by water cooling after stopping, and puts in the 2000g methyl alcohol, filters the white powder of separating out., behind the white powder of cleaning and filtering on the slurries, filter with the methyl alcohol of 400g 2 times, 50 ℃ dry 17 hours down, obtain the resin (74g, productive rate 74%) of white powder.The Mw=7900 of this resin, Mw/Mn=1.45, repetitive, each the repetitive containing ratio that is compound (S1-24), compound (S2-24), compound (S3-24) expression are the multipolymer of 34.1: 51.0: 14.9 (mole %).This resin is resin (A-24).
Synthesis example 25
Preparation in the 2-of 37.5g butanone, dissolve 9.01g (50 moles of %) compound (S1-25), 10.98g (50 moles of %) compound (S2-25) monomer solution (1), in the 2-of 16.0g butanone the dimethyl 2 of dissolving 0.844g, the solution (2) of 2 '-azo two (2 Methylpropionic acid ester), and then monomer solution (1) 5.75g, solution (2) 1.05g that prepare before in the three-neck flask of the 300ml of the 2-butanone that has added 0.704g pyrazoles-1-carbodithioic acid cyano group dimethyl methyl esters, 3.8g, adding, carry out nitrogen purge with the decompression substitution method then.After the nitrogen purge, while stirring with reactor 80 ℃ of heating, after 15 minutes, use fluid filling pump with 3 hours dropping monomer solution (1) 51.79g, solution (2) 6.16g.After dripping beginning, be determined at Mw, Mw/Mn after 1,2,3 hour, to the conversion ratio of polymkeric substance.
Stirred again 4 hours after dripping.Measure to stir Mw, the Mw/Mn of back after 2,4 hours, to the conversion ratio of polymkeric substance.
After polymerization stops, polymeric solution is cooled to below 30 ℃ by placing cooling.The dimethyl 2 that adds 2.277g then in polymeric solution, 2 '-azo two (2 Methylpropionic acid ester) heats under 80 ℃ and stirred 3 hours, carries out end processing.Measure Mw, Mw/Mn after terminal the processing, to the conversion ratio of polymkeric substance.
Behind the reaction terminating, solution is cooled to below 30 ℃, joins in the isopropyl alcohol of 1000g, filter the white powder of separating out by placing cooling.The isopropyl alcohol that uses 500g filters behind the white powder of twice cleaning and filtering on the slurries, and drying is 17 hours under 60 ℃, obtains the polymkeric substance (A-25) (17g, productive rate 85%) of white powder.The result of following response all is shown in Table 1.
Table 1
Figure G2003801077532D00571
Synthesis example 26
Figure G2003801077532D00572
The compound (S1-26) of 7.07g (40 moles of %) is dissolved in preparation in the 2-of 37.5g butanone, the compound (S2-26) of (10.78g 50 moles of %), the monomer solution (1) of the compound (S3-26) of (2.13g 10 moles of %), the dimethyl 2 of dissolving 0.844g in the 2-of 16.0g butanone, the solution (2) of 2 '-azo two (2 Methylpropionic acid ester), and then adding 0.704g pyrazoles-1-carbodithioic acid cyano group dimethyl methyl esters, 3.8g the three-neck flask of 300ml of 2-butanone in monomer solution (1) 5.75g for preparing before adding, solution (2) 1.05g carries out nitrogen purge with the decompression substitution method then.After the nitrogen purge, while stirring with reactor 80 ℃ of heating, after 15 minutes, use fluid filling pump with 3 hours dropping monomer solution (1) 51.79g, solution (2) 6.16g.After dripping beginning, be determined at Mw, Mw/Mn after 1,2,3 hour, to the conversion ratio of polymkeric substance.
Stirred again 4 hours after dripping.Measure to stir Mw, the Mw/Mn of back after 2,4 hours, to the conversion ratio of polymkeric substance.
After polymerization stops, polymeric solution is cooled to below 30 ℃ by placing cooling.The dimethyl 2 that adds 2.23g then in polymeric solution, 2 '-azo two (2 Methylpropionic acid ester) heats under 80 ℃ and stirred 3 hours, carries out end processing.Measure Mw, Mw/Mn after terminal the processing, to the conversion ratio of polymkeric substance.
Behind the reaction terminating, solution is cooled to below 30 ℃, joins in the isopropyl alcohol of 1000g, filter the white powder of separating out by placing cooling.The isopropyl alcohol that uses 500g filters behind the white powder of twice cleaning and filtering on the slurries, and drying is 17 hours under 60 ℃, obtains the polymkeric substance (A-26) (16g, productive rate 80%) of white powder.The result of following response all is shown in Table 2.
Table 2
Figure G2003801077532D00581
Compare synthesis example 1
The compound (S1-8) of the dissolving 35.88g (35 mole %) identical, the compound (S2-8) of 48.61g (50 moles of %), the compound (S3-8) of 15.51g (15 moles of %) in 200g toluene with synthesis example 8, in the three-neck flask that toluene and the azoisobutyronitrile of 100g joined 1000 milliliters, with nitrogen purge 30 minutes.After the nitrogen purge, reactor is heated to 110 ℃ while stirring, uses tap funnel with 3 hours above-mentioned monomer solutions of dropping preprepared.To drip the time that beginning begins as polymerization, implemented polyreaction 48 hours.Polymerization is cooled to polymeric solution below 30 ℃ by water cooling after stopping, and puts in the 2000g methyl alcohol, filters the white powder of separating out., after cleaning the white powder that filters for 2 times on the slurries, filter with the methyl alcohol of 400g, 50 ℃ dry 17 hours down, obtain the resin (70g, productive rate 70%) of white powder.The Mw=9500 of this resin, Mw/Mn=2.20, repetitive, each the repetitive containing ratio that is compound (S1-8), compound (S2-8), compound (S 3-8) expression are the multipolymer of 33.2: 52.1: 14.7 (mole %).This resin is resin (AC-1).
Embodiment 1～26, comparative example 1
Each polymkeric substance that obtains in synthesis example 1～synthesis example 26 and the comparison synthesis example 1, acid producing agent and other compositions shown below are mixed with the ratio shown in the table 3, obtain each radiation-sensitive resin composition solution.The radiation-sensitive resin composition solution that obtains is carried out various evaluations.Evaluation result is shown in Table 4.Here, part does not specify and is weight portion.
Acid producing agent (B)
(B-1): triphenylsulfonium, nine fluoro normal butane sulfonate
Acid diffusion control agent (C)
(C-1): triethanolamine
Solvent (D)
(D-1): propylene glycol methyl ether acetate
(D-2): cyclohexanone
Table 3
Table 4
Figure G2003801077532D00611
Radiation-sensitive resin composition of the present invention is high and sensitivity, resolution, anti-dry corrosion, good as the basic physical properties of the resist of pattern form etc. to the transparency of radioactive ray, particularly the dissolubility to solvent against corrosion is good, the roughness of back pattern sidewalls of reduce developing, thereby can very suitably be applicable in the manufacturing of the semiconductor equipment that expectability from now on can further miniaturization.

Claims (8)

1. ArF excimer laser radiation-sensitive resin composition; It is characterized in that this radiation-sensitive resin composition contains the resin and the radiation-sensitive acid that close the acid dissociation group and produces agent; Insoluble or alkali slightly solubility becomes the alkali ease of solubility to this resin that contains the acid dissociation group by alkali by the acid effect; The above-mentioned resin that contains the acid dissociation group contains the repetitive of following formula (1) expression; The ratio of weight average molecular weight and number-average molecular weight, be that weight-average molecular weight/number-average molecular weight is less than 1.5; Use the active free radical polymerization initator to obtain
At least a kind the repetitive that the above-mentioned resin that contains the acid dissociation group contains the repetitive of formula (1) expression and is selected from the repetitive group of formula (2 ')～formula (7 ') expression;
Described active free radical polymerization initiating agent is the compound of following formula (8) expression,
Figure F2003801077532C00011
In the formula (1), R 1Represent hydrogen, methyl, trifluoromethyl or methylol independently of each other, R 2Represent that independently of each other carbon number is that 4～20 1 valency alicyclic hydrocarbon radical or carbon number are 1～4 straight or branched alkyl, and R 2At least one be this alicyclic hydrocarbon radical, or any 2 R 2Mutually combine, it is 4～20 divalent alicyclic hydrocarbon radical that the carbon atom that comprises combination separately forms carbon number together, remaining R 2Be that the alkyl of 1～4 straight or branched or carbon number are 4～20 1 valency alicyclic hydrocarbon radical for carbon number,
In formula (2 ')～formula (7 '),
A represents singly-bound or optional has alkylidene, list or two aklylene glycol bases, an alkylidene ester group that carbon number is 1～6 substituent straight or branched,
B represents singly-bound or also can have carbon number is 1～3 substituent alkylidene, alkoxy, oxygen atom,
E represents that singly-bound or carbon number are 1～3 divalent alkyl,
R 3Represent independently of each other hydroxyl, cyano group, carboxyl ,-COOR 5, or-Y-R 6, R 5Be that the alkyl of 1～4 straight or branched or carbon number are 3～20 alicyclic alkyl for hydrogen atom or carbon number, Y represents that independently of each other singly-bound or carbon number are 1～3 divalent alkylidene, R 6Represent independently of each other hydrogen atom, hydroxyl, cyano group or-COOR 7Base, at least one R 3Not hydrogen atom, R 7The alkyl of the straight or branched of expression hydrogen atom or carbon number 1～4 or carbon number are 3～20 alicyclic alkyl,
G represents that singly-bound, carbon number are that the alkylidene of 1～6 straight or branched or carbon number are 4～20 alicyclic hydrocarbon radical, aklylene glycol base, alkylidene ester group,
J, L, N, M represent singly-bound respectively independently, also can have carbon number is 1～20 substituent straight chain, side chain, the alkylidene of ring-type, aklylene glycol base, alkylidene ester group, and p is 0 or 1,
R 4Expression hydrogen atom, carbon number are that 1～4 straight or branched alkyl, alkoxy, hydroxy alkyl, carbon number are the alicyclic hydrocarbon radical of 3～20 divalent, and q is 1 or 2;
In the formula (8), the optional carbon number that contains ester group, ether, amino, amide group of R ' expression is 1～15 alkyl or aryl, Y represents singly-bound combination, oxygen atom, nitrogen-atoms or sulphur atom, R " represent that the optional carbon number that contains ester group, ether, amino is 1～15 alkyl or aryl.
2. according to the radiation-sensitive resin composition of claim 2 record, it is characterized in that at least 1 repetitive of the repetitive group that the above-mentioned above-mentioned formula (2 ') that the is selected from～formula (7 ') that contains the resin of acid dissociation group is represented is the repetitive of formula (2 ') expression.
3. according to the radiation-sensitive resin composition of claim 1 or 2 records, it is characterized in that the ratio of above-mentioned repetitive (1) is 15～70 moles of % with respect to whole repetitives.
4. according to the radiation-sensitive resin composition of claim 3 record, it is characterized in that the above-mentioned resin that contains the acid dissociation group be constitute this resin each repetitive atactic polymerization and polymkeric substance.
5. according to the radiation-sensitive resin composition of claim 1 record, it is characterized in that producing the above-mentioned active free radical polymerization initiating agent of the terminal processing of agent with hot radical.
6. according to the radiation-sensitive resin composition of claim 1 record, wherein above-mentioned radiation-sensitive acid produces agent and contains at least a compound that is selected from triphenylsulfonium salt compound, 4-cyclohexyl phenyl diphenyl sulfonium salt compound, 4-tert-butyl-phenyl diphenyl sulfonium salt compound and three (4-tert-butyl-phenyl) sulfonium salt compound.
7. according to the radiation-sensitive resin composition of claim 1 record, the agent of the further acid mixture diffusion control of wherein above-mentioned radiation-sensitive resin composition, this acid diffusion control agent contains organic compounds containing nitrogen.
8. according to the radiation-sensitive resin composition of claim 2 record, wherein, in the repetitive of above-mentioned formula (1) expression, formation-C (R 2) 3Functional group's side chain, be 1-methyl isophthalic acid-cyclopentyl, 1-ethyl-1-cyclopentyl, 1-methyl isophthalic acid-cyclohexyl or 1-ethyl-1-cyclohexyl.
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